Storage container storing treatment liquid for manufacturing semiconductor

ABSTRACT

A storage container storing a treatment liquid for manufacturing a semiconductor. The treatment liquid for manufacturing a semiconductor includes: one compound (A) that satisfies the requirement (a); one compound (B) or two or more compounds (B) that satisfy the requirement (b); and one inorganic matter (C) or two or more inorganic matters (C) having any element selected from the group consisting of Al, B, S, N, and K. Here, a total content of the compound (B) in the treatment liquid is 10 −10  to 0.1 mass %, and a ratio P of the inorganic matter (C) to the compound (B) is 10 3  to 10 −6 .

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation Application of and claims thepriority benefit of a prior U.S. application Ser. No. 16/143,492, filedon Sep. 27, 2018, now allowed. The prior application Ser. No. 16/143,492is a Continuation Application of PCT Application No. PCT/JP2017/010619,filed Mar. 16, 2017, and based upon and claiming the benefit of priorityfrom Japanese Patent Applications No. 2016-073256, filed Mar. 31, 2016;and No. 2017-045815, filed Mar. 10, 2017, the entire contents of all ofwhich are incorporated herein by reference.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to a treatment liquid for manufacturing asemiconductor, such as a developer, a rinsing liquid, a pre-wet liquid,or a peeling liquid, that is used in manufacturing steps of asemiconductor device, a method of manufacturing the treatment liquid formanufacturing a semiconductor, a pattern forming method, and a method ofmanufacturing an electronic device.

2. Description of the Related Art

The manufacturing steps of a semiconductor device include various stepssuch as a lithography step, an etching step, an ion implantation step,or a peeling step. In general, a step of treating unnecessary organicmatters and inorganic matters using a treatment liquid is provided afterthe end of each step or before the start of the next step. For example,a development step of treating an exposed resist film using a developer,a peeling step of treating a resist remaining on a surface of a treatedsubstrate using a peeling liquid, or a rinsing step of further purifyingthe surface using a rinsing liquid after the peeling step or thedevelopment step may be provided.

Various treatment liquids, such as a developer, a rinsing liquid, apre-wet liquid, or a peeling liquid used in the manufacturing steps of asemiconductor device (hereinafter, referred to as “treatment liquids formanufacturing a semiconductor”) are required to have high purity. Alongwith a reduction in size and functionality improvement ofsemiconductors, market needs for high-purity treatment liquids have beenincreasing, and the market is expected to expand in the future.

In order for the treatment liquid for manufacturing a semiconductor tohave high purity, low metal concentration and low particle concentrationare basic requirements. For example, JP2015-84122A discloses a techniquecapable of reducing the formation of particles in an organic developer.In addition, metal in the treatment liquid causes a phenomenon calledmigration in which the metal is diffused into a target material during atreatment. The migration inhibits transmission of an electrical signaland causes defects such as short-circuiting. In addition, this metal mayfunction as a nucleus such that dust remains as a residue after atreatment, which causes deterioration of lithographic performance or theoccurrence of defects. As a result, there is an adverse effect on theformation of a fine resist pattern or a semiconductor element. Under theabove-described circumstances, higher purity of the treatment liquid formanufacturing a semiconductor has been strongly desired.

SUMMARY OF THE INVENTION

The latest treatment liquid for manufacturing a semiconductor that isused in the current semiconductor manufacturing industry achieves highpurity to some extent. For example, in a rinsing liquid includingisopropanol (IPA) (manufactured by FEUS) that is famous for high purityand low metal concentration, the total metal concentration is severaltens to sever hundreds of mass ppt (parts per trillion). However,performance required in the future is, for example, a metalconcentration of 10 mass ppt or lower, which cannot be satisfied underthe present circumstances.

The present invention has been developed under the above-describedcircumstances, and an object thereof is to provide a treatment liquidfor manufacturing a semiconductor with which deterioration oflithographic performance or the occurrence of defects is suppressed suchthat a fine resist pattern or a fine semiconductor element can bemanufactured, and a method of manufacturing the treatment liquid formanufacturing a semiconductor. Another object of the present inventionis to provide a pattern forming method using the treatment liquid formanufacturing a semiconductor and a method of manufacturing asemiconductor element including the pattern forming method.

One aspect of the present invention is as follows.

[1] A treatment liquid for manufacturing a semiconductor comprising:

one compound (A) that satisfies the following requirement (a);

one compound (B) or two or more compounds (B) that satisfy the followingrequirement (b); and

one inorganic matter (C) or two or more inorganic matters (C) having anyelement selected from the group consisting of Al, B, S, N, and K,

in which a total content of the compound (B) in the treatment liquid is10⁻¹⁰ to 0.1 mass %,

a ratio P of the inorganic matter (C) to the compound (B) represented bythe following Expression I is 10³ to 10⁻⁶,

the requirement (a): a compound that is selected from the groupconsisting of an alcohol compound, a ketone compound, and an estercompound and of which a content in the treatment liquid is 90.0 to99.9999999 mass %,

the requirement (b): a compound that is selected from the groupconsisting of an alcohol compound having 6 or more carbon atoms, aketone compound, an ester compound, an ether compound, and an aldehydecompound and of which a content in the treatment liquid is 10⁻¹¹ to 0.1mass %, and

P=[Total Mass of Inorganic Matter (C)]/[Total Mass of Compound (B)]  Expression I.

[2] The treatment liquid for manufacturing a semiconductor according to[1], in which the inorganic matter (C) is a compound having any elementselected from the group consisting of Al, B, and S.

[3] The treatment liquid for manufacturing a semiconductor according to[1] or [2], in which a content of the one inorganic matter (C) or eachof the two or more inorganic matters (C) in the treatment liquid formanufacturing a semiconductor is 0.0001 to 100 mass ppb.

[4] The treatment liquid for manufacturing a semiconductor according toany one of [1] to [3],

in which a content of the one inorganic matter (C) or each of the two ormore inorganic matters (C) in the treatment liquid for manufacturing asemiconductor is 0.001 to 100 mass ppb.

[5] The treatment liquid for manufacturing a semiconductor according toany one of [1] to [4],

in which the treatment liquid for manufacturing a semiconductorcomprises Na, Ca, and Fe, and

a content of each of Na, Ca, and Fe is 0.01 mass ppt to 1000 mass ppb.

[6] The treatment liquid for manufacturing a semiconductor according toany one of [1] to [5],

in which a total content of metal particles measured by a SNP-ICP-MSmethod is 0.001 to 100 mass ppt.

[7] The treatment liquid for manufacturing a semiconductor according toany one of [1] to [6],

in which a total content of metal particles measured by a SNP-ICP-MSmethod is 1 to 100 mass ppt.

[8] The treatment liquid for manufacturing a semiconductor according toany one of [1] to [7],

in which the treatment liquid for manufacturing a semiconductorcomprises at least one of compounds represented by the followingFormulae I to V as the compound (B),

in Formula I, R₁ and R₂ each independently represent an alkyl group or acycloalkyl group or may be bonded to each other to form a ring,

in Formula II, R₃ and R₄ each independently represent a hydrogen atom,an alkyl group, an alkenyl group, a cycloalkyl group, or a cycloalkenylgroup or may be bonded to each other to form a ring, and both R₃ and R₄do not represent a hydrogen atom,

in Formula III, R₅ represents an alkyl group or a cycloalkyl group,

in Formula IV, R₆ and R₇ each independently represent an alkyl group ora cycloalkyl group or may be bonded to each other to form a ring,

in Formula V, R₈ and R₉ each independently represent an alkyl group or acycloalkyl group or may be bonded to each other to form a ring, and Lrepresents a single bond or an alkylene group.

[9] The treatment liquid for manufacturing a semiconductor according toany one of [1] to [8],

in which a ratio Q of the compound (A) to the compound (B) representedby the following Expression II is 10⁴ to 10¹⁰,

Q=[Total Mass of Compound (A)]/[Total Mass of Compound (B)]  ExpressionII.

[10] A treatment liquid for manufacturing a semiconductor comprising:

two or more treatment liquids for manufacturing a semiconductor amongthe treatment liquids for manufacturing a semiconductor according to [1]to [9].

[11] The treatment liquid for manufacturing a semiconductor according toany one of [1] to [10],

in which the treatment liquid for manufacturing a semiconductor is adeveloper.

[12] The treatment liquid for manufacturing a semiconductor according toany one of [1] to [10],

in which the treatment liquid for manufacturing a semiconductor is arinsing liquid.

[13] The treatment liquid for manufacturing a semiconductor according toany one of [1] to [10],

wherein the treatment liquid for manufacturing a semiconductor is apre-wet liquid.

[14] A method of manufacturing the treatment liquid for manufacturing asemiconductor according to any one of [1] to [13], the methodcomprising:

obtaining a crude liquid including the compound (A), the compound (B),and the inorganic matter (C) by causing one raw material or two or moreraw materials to react with each other in the presence of a catalyst soas to synthesize the compound (A); and

purifying the crude liquid.

[15] A pattern forming method comprising:

a step of applying an actinic ray-sensitive or radiation-sensitive resincomposition to a substrate to form an actinic ray-sensitive orradiation-sensitive film;

a step of exposing the actinic ray-sensitive or radiation-sensitivefilm; and

a step of treating the substrate or the actinic ray-sensitive orradiation-sensitive film using the treatment liquid for manufacturing asemiconductor according to any one of [1] to [13].

[16] The pattern forming method according to [15],

in which the pattern forming method comprises at least a step ofdeveloping the actinic ray-sensitive or radiation-sensitive film byusing the treatment liquid for manufacturing a semiconductor as adeveloper as the step of treating the substrate or the actinicray-sensitive or radiation-sensitive film using the treatment liquid formanufacturing a semiconductor.

[17] The pattern forming method according to [15] or [16],

in which the pattern forming method comprises at least a step ofcleaning the actinic ray-sensitive or radiation-sensitive film by usingthe treatment liquid for manufacturing a semiconductor as a rinsingliquid as the step of treating the substrate or the actinicray-sensitive or radiation-sensitive film using the treatment liquid formanufacturing a semiconductor.

[18] The pattern forming method according to any one of [15] to [17],

in which the pattern forming method comprises at least a step oftreating the substrate by using the treatment liquid for manufacturing asemiconductor as a pre-wet liquid as the step of treating the substrateor the actinic ray-sensitive or radiation-sensitive film using thetreatment liquid for manufacturing a semiconductor.

[19] The pattern forming method according to any one of [15] to [18],

in which in a case where the actinic ray-sensitive orradiation-sensitive film before exposure is dipped in the treatmentliquid for manufacturing a semiconductor, a dissolution rate of theactinic ray-sensitive or radiation-sensitive film at 23° C. is 0.0016 to0.33 nm/sec.

[20] A method of manufacturing an electronic device comprising:

the pattern forming method according to any one of [15] to [19].

According to the present invention, it is possible to provide atreatment liquid for manufacturing a semiconductor with whichdeterioration of lithographic performance or the occurrence of defectsis suppressed such that a fine resist pattern or a fine semiconductorelement can be manufactured, and a method of manufacturing the treatmentliquid for manufacturing a semiconductor. In addition, according to thepresent invention, it is possible to provide a pattern forming methodusing the treatment liquid for manufacturing a semiconductor and amethod of manufacturing a semiconductor element including the patternforming method.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram showing an aspect of a manufacturingdevice that can be used in a method of manufacturing a treatment liquidaccording to an embodiment of the present invention.

FIG. 2 is a schematic diagram showing another aspect of themanufacturing device that can be used in the method of manufacturing thetreatment liquid according to the embodiment of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In this specification, unless specified as a substituted group or as anunsubstituted group, a group (atomic group) denotes not only a grouphaving no substituent but also a group having a substituent. Forexample, “alkyl group” denotes not only an alkyl group having nosubstituent (unsubstituted alkyl group) but also an alkyl group having asubstituent (substituted alkyl group).

In this specification, “actinic ray” or “radiation” denotes, forexample, a bright light spectrum of a mercury lamp, a far ultravioletray represented by excimer laser, an extreme ultraviolet lithography ray(EUV ray), an X-ray, or an electron beam (EB). In addition, in thepresent invention, “light” denotes an actinic ray or radiation.

In addition, in this specification, unless specified otherwise,“exposure” denotes not only exposure using a mercury lamp, a farultraviolet ray represented by excimer laser, an X-ray, an EUV ray, orthe like but also drawing using a corpuscular beam such as an electronbeam or an ion beam.

In this specification, “(meth)acrylate” represents “at least one ofacrylate or methacrylate”. In addition, “(meth)acrylic acid” represents“at least one of acrylic acid or methacrylic acid”. In addition, in thisspecification, numerical ranges represented by “to” include numericalvalues before and after “to” as lower limit values and upper limitvalues. Hereinafter, embodiments of the present invention will bedescribed in detail.

<Treatment Liquid for Manufacturing Semiconductor>

As described above, in manufacturing steps of a semiconductor deviceincluding an lithography step, an etching step, an ion implantationstep, and a peeling step, “treatment liquid for manufacturing asemiconductor” according to the present invention is a treatment liquidused for treating an organic matter before the end of each step or afterthe start of the next step, and is specifically a treatment liquid usedas a developer, a rinsing liquid, a pre-wet liquid, or a peeling liquid.

The treatment liquid for manufacturing a semiconductor according to thepresent invention (for example, also referred to as “treatment liquidaccording to the present invention”) includes: one compound (A) thatsatisfies the following requirement (a); at least one compound (B) thatsatisfies the following requirement (b); and at least one inorganicmatter (C) having any element selected from the group consisting of Al,B, S, N, and K.

Requirement (a): a compound that is selected from the group consistingof an alcohol compound, a ketone compound, and an ester compound and ofwhich a content in the treatment liquid according to the presentinvention is 90.0 to 99.9999999 mass %

Requirement (b): a compound that is selected from the group consistingof an alcohol compound having 6 or more carbon atoms, a ketone compound,an ester compound, an ether compound, and an aldehyde compound and ofwhich a content in the treatment liquid according to the presentinvention is 10⁻¹¹ to 0.1 mass %

The compound (A) is a major component of which the content in thetreatment liquid according to the present invention is 90.0 to99.9999999 mass %, and the content thereof is, for example, preferably99.999 to 99.9999999 mass % and more preferably 99.9999 to 99.9999999mass %.

In addition, the treatment liquid according to the present invention maybe a combination of the compound (A) and another compound. In this case,the content of the other compound is, for example, preferably 0.01 to5.00 mass % and more preferably 0.1 to 2.00 mass %.

In this case, examples of the other compound include dimethyl sulfoxide.

The compound (B) is included in the treatment liquid according to thepresent invention as an impurity, and the total content thereof is 10⁻¹⁰to 0.1 mass % with respect to the total mass of the treatment liquid.Here, in a case where one compound (B) in which the content satisfiesthe requirement (b), that is, in a range of 10⁻¹¹ to 0.1 mass % ispresent in the treatment liquid, the total content of the compound (B)refers to the content of the one compound (B). In addition, in a casewhere two or more compounds (B) in which the content satisfies thecontent requirement described in the requirement (b) are present in thetreatment liquid, the total content of the compound (B) refers to thetotal content of the two or more compounds (B).

The content of the compound (B) described in the requirement (b) ispreferably 10⁻¹⁰ to 10⁻⁴ mass % and more preferably 10⁻¹⁰ to 10⁻⁵ mass%.

In the treatment liquid according to the present invention, theinorganic matter (C) having any element selected from the groupconsisting of Al, B, S, N, and K is incorporated during the synthesis ofthe treatment liquid according to the present invention and is mainlyderived from a catalyst.

In one aspect, the treatment liquid according to the present inventionincludes a compound having any element selected from the groupconsisting of Al, B, and S as the inorganic matter (C).

Most of the compound (B) and the inorganic matter (C) are removed in apurification step of the treatment liquid, but a slight amount of thecompound (B) and the inorganic matter (C) remain in the purifiedtreatment liquid.

The present invention has been developed based on the finding that aratio of the inorganic matter (C) to the compound (B) in the treatmentliquid for manufacturing a semiconductor has a significant impact onlithographic performance or defect performance, and has onecharacteristic in that a P value represented by the following ExpressionI that is the ratio of the inorganic matter (C) to the compound (B) isin a range of 10³ to 10⁻⁶.

P=[Total Mass of Inorganic Matter (C)]/[Total Mass of Compound(B)]  Expression I.

In a case where the ratio P of the inorganic matter (C) to the compound(B) is in a range of 10³ to 10⁻⁶, deterioration of lithographicperformance or the occurrence of defects is suppressed such that a fineresist pattern or a fine semiconductor element can be manufactured. Themechanism of this phenomenon is not necessarily clear but is presumed tobe as follows. In a case where a balance between the compound (B) andthe inorganic matter (C) in the treatment liquid is lost, for example,during a treatment using each treatment liquid such as a developer, arinsing liquid, a pre-wet liquid, or a peeling liquid, an uniquephenomenon causing deterioration of lithographic performance or theoccurrence of defects occurs.

The P value represented by Expression I that is the ratio of theinorganic matter (C) to the compound (B) is preferably 10³ to 10⁻⁵ andmore preferably 10² to 10⁻⁴.

The compound (B) is an impurity in which the total content is in a rangeof 10⁻¹⁰ to 0.1 mass % with respect to the total mass of the treatmentliquid. However, from the viewpoint of improving lithographicperformance and suppressing defects, it is preferable that a ratio Q ofthe compound (A) to the compound (B) represented by the followingExpression II is 10⁴ to 10¹⁰.

Q=[Total Mass of Compound (A)]/[Total Mass of Compound (B)]  ExpressionII.

The mechanism of this phenomenon is not clear, but it is verified thatin a case where the ratio Q of the compound (A) to the compound (B) isin the above-described range, the effects of the present invention areimproved.

The Q value represented by Expression II that is the ratio of thecompound (A) to the compound (B) is more preferably 10⁵ to 10¹⁰ andstill more preferably 106 to 10¹⁰.

In the treatment liquid according to the present invention, the contentof the inorganic matter (C) is preferably 0.0001 to 100 mass ppb (partsper billion) and more preferably 0.001 to 100 mass ppb with respect tothe total mass of the treatment liquid. In a case where the treatmentliquid according to the present invention includes two or more inorganicmatters (C), the content of each of the inorganic matters (C) ispreferably 0.0001 to 100 mass ppb and more preferably 0.001 to 100 massppb.

In a case where the concentration of each of the inorganic matters (C)is 100 mass ppb or lower, the occurrence of defects caused by thesecompounds remaining on a substrate as nuclei of residual componentsduring a treatment can be suppressed.

On the other hand, in general, it is considered that, the lower theconcentration of the inorganic matter (C), the better. However, it isverified that, in a case where the concentration of the inorganic matter(C) is lower than 0.001 mass ppb, the amount of defects tends toincrease again. The mechanism of this phenomenon is not necessarilyclear but is presumed to be as follows. In a case where the inorganicmatter (C) is removed from a substrate, the inorganic matter (C) isremoved along with the compound (B) as an aggregate of ions or acompound. Therefore, in a case where the concentration of the inorganicmatter (C) is excessively low, the removal rate of the inorganic matter(C) and the compound (B) deteriorates, and the compound (B) and theinorganic matter (C) remain on the substrate, which cause the occurrenceof defects.

As described above, the compound (A) included in the treatment liquidaccording to the present invention is a compound selected from the groupconsisting of an alcohol compound, a ketone compound, and an estercompound. The treatment liquid according to the present inventionincludes one compound or two or more compounds.

Examples of the alcohol compound include: an alcohol (monohydricalcohol) such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol,2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol,2-pentanol, 1-hexanol, 3-methyl-3-pentanol, cyclopentanol,2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol,2-methyl-3-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol,4-methyl-3-pentanol, cyclohexanol, or 3-methoxy-1-butanol; a glycolsolvent such as ethylene glycol, diethylene glycol, or triethyleneglycol; and an glycol ether solvent having a hydroxyl group such asethylene glycol monomethyl ether, propylene glycol monomethyl ether(PGME; synonym: 1-methoxy-2-propanol), diethylene glycol monomethylether, methoxy methyl butanol, ethylene glycol monoethyl ether, ethyleneglycol monopropyl ether, or ethylene glycol monobutyl ether.

Examples of the ketone compound include acetone, 1-hexanone, 2-hexanone,cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone,acetylacetone, acetonylacetone, acetyl carbinol, propylene carbonate,and γ-butyrolactone. The ketone compound as the compound (A) includes adiketone compound.

Examples of the ester compound include methyl acetate, ethyl acetate,butyl acetate, isobutyl acetate, propyl acetate, isopropyl acetate,ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethylether acetate (PGMEA; synonym: 1-methoxy-2-acetoxy propnae), ethyleneglycol monoethyl ether acetate, ethylene glycol monopropyl etheracetate, ethylene glycol monobutyl ether acetate, methyl formate, ethylformate, butyl formate, propyl formate, ethyl lactate, propyl lactate,ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate,ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethylacetoacetate, methyl propionate, ethyl propionate, propyl propionate,and isopropyl propionate.

In one aspect, the compound (A) may be a mixture of compounds having thesame number of carbon atoms and different structures, for example,isomers. As the compounds having the same number of carbon atoms anddifferent structures, only one kind may be included, and a plurality ofkinds may be included.

In one aspect, the flash point of the compound (A) is preferably 80° C.or lower, more preferably 75° C. or lower, and still more preferably 65°C. or lower. In addition, the lower limit value of the flash point isnot particularly limited and is, for example, preferably 23° C. orhigher.

As described above, the compound (B) included in the treatment liquidaccording to the present invention is a compound selected from the groupconsisting of an alcohol compound having 6 or more carbon atoms, aketone compound, an ester compound, an ether compound, and an aldehydecompound. The treatment liquid according to the present inventionincludes one compound or two or more compounds. The number of carbonatoms in the compound (B) is preferably 6 to 12 and more preferably 6 to10.

In one aspect of the present invention, it is preferable that thecompound (B) is at least one of compounds represented by the followingFormulae I to V.

In Formula I, R₁ and R₂ each independently represent an alkyl group or acycloalkyl group or may be bonded to each other to form a ring.

As the alkyl group and the cycloalkyl group represented by R₁ and R₂, analkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 6to 12 carbon atoms, is preferable, and an alkyl group having 1 to 8carbon atoms or a cycloalkyl group having 6 to 8 carbon atoms is morepreferable.

The ring which is formed by R₁ and R₂ being bonded to each other ispreferably a lactone ring, more preferably a 4-membered to 9-memberedlactone ring, and still more preferably a 4-membered to 6-memberedlactone ring.

R₁ and R₂ satisfy a relationship in which the number of carbon atoms inthe compound represented by Formula I is 6 or more.

In Formula II, R₃ and R₄ each independently represent a hydrogen atom,an alkyl group, an alkenyl group, a cycloalkyl group, or a cycloalkenylgroup or may be bonded to each other to form a ring. Both R₃ and R₄ donot represent a hydrogen atom.

As the alkyl group represented by R₃ and R₄, for example, an alkyl grouphaving 1 to 12 carbon atoms is preferable, and an alkyl group having 1to 8 carbon atoms is more preferable.

As the alkenyl group represented by R₃ and R₄, for example, an alkenylgroup having 2 to 12 carbon atoms is preferable, and an alkenyl grouphaving 2 to 8 carbon atoms is more preferable.

As the cycloalkyl group represented by R₃ and R₄, for example, acycloalkyl group having 6 to 12 carbon atoms is preferable, and acycloalkyl group having 6 to 8 carbon atoms is more preferable.

As the cycloalkenyl group represented by R₃ and R₄, for example, acycloalkenyl group having 3 to 12 carbon atoms is preferable, and acycloalkenyl group having 6 to 8 carbon atoms is more preferable.

The ring which is formed by R₃ and R₄ being bonded to each other is acyclic ketone structure and may be saturated cyclic ketone orunsaturated cyclic ketone. This cyclic ketone is preferably a 6-memberedto 10-membered ring and more preferably a 6-membered to 8-membered ring.

R₃ and R₄ satisfy a relationship in which the number of carbon atoms inthe compound represented by Formula II is 6 or more.

In Formula III, R₅ represents an alkyl group or a cycloalkyl group,

The alkyl group represented by R₅ is an alkyl group having 6 or morecarbon atoms, preferably an alkyl group having 6 to 12 carbon atoms, andmore preferably an alkyl group having 6 to 10 carbon atoms.

This alkyl group may have an ether bond in a chain or may have asubstituent such as a hydroxy group.

The cycloalkyl group represented by R₅ is a cycloalkyl group having 6 ormore carbon atoms, preferably a cycloalkyl group having 6 to 12 carbonatoms, and more preferably a cycloalkyl group having 6 to 10 carbonatoms.

In Formula IV, R₆ and R₇ each independently represent an alkyl group ora cycloalkyl group or may be bonded to each other to form a ring.

As the alkyl group represented by R₆ and R₇, for example, an alkyl grouphaving 1 to 12 carbon atoms is preferable. Further, an alkyl grouphaving 1 to 8 carbon atoms is more preferable.

As the cycloalkyl group represented by R₆ and R₇, for example, acycloalkyl group having 6 to 12 carbon atoms is preferable, and acycloalkyl group having 6 to 8 carbon atoms is more preferable.

The ring which is formed by R₆ and R₇ being bonded to each other is acyclic ether structure. This cyclic ether structure is preferably a4-membered to 8-membered ring and more preferably a 5-membered to7-membered ring.

R₆ and R₇ satisfy a relationship in which the number of carbon atoms inthe compound represented by Formula IV is 6 or more.

In Formula V, R₈ and R₉ each independently represent an alkyl group or acycloalkyl group or may be bonded to each other to form a ring. Lrepresents a single bond or an alkylene group.

As the alkyl group represented by R₈ and R₉, for example, an alkyl grouphaving 6 to 12 carbon atoms is preferable, and an alkyl group having 6to 10 carbon atoms is more preferable.

As the cycloalkyl group represented by R₈ and R₉, for example, acycloalkyl group having 6 to 12 carbon atoms is preferable, and acycloalkyl group having 6 to 10 carbon atoms is more preferable.

The ring which is formed by R₈ and R₉ being bonded to each other is acyclic diketone structure. This cyclic diketone structure is preferablya 6-membered to 12-membered ring and more preferably a 6-membered to10-membered ring.

As the alkylene group represented by L, for example, an alkylene grouphaving 1 to 12 carbon atoms is preferable, and an alkylene group having1 to 10 carbon atoms is more preferable.

R₈, R₉, and L satisfy a relationship in which the number of carbon atomsin the compound represented by Formula V is 6 or more.

Specific examples of the compound (B) include the following compounds.

In one aspect, the treatment liquid according to the present inventionincludes Na, Ca, and Fe, and the content of each of Na, Ca, and Fe ispreferably 0.01 mass ppt to 1000 mass ppb. Na, Ca, and Fe are metalatoms which are incorporated during various processes until thetreatment liquid according to the present invention is synthesized. In acase where the concentration of each of the metal atoms is 1000 mass ppbor lower, the occurrence of defects caused by these metal atomsremaining on a substrate as nuclei of residual components during atreatment can be suppressed.

On the other hand, in general, it is considered that, the lower theconcentration of each of the metal atoms, the better. However, it isverified that, in a case where the concentration of each of the metalatoms is lower than 0.01 mass ppt, the amount of defects tends toincrease again. The mechanism of this phenomenon is not necessarilyclear but is presumed to be as follows. In a case where Na, Ca, or Fe isremoved from a substrate, Na, Ca, or Fe is removed along with thecompound (B) and/or the compound (C) as an aggregate of atoms.Therefore, in a case where the concentration of Na, Ca, or Fe isexcessively low, the removal rate of the compound (B) and/or thecompound (C) and Na, Ca, or Fe deteriorates, and Na, Ca, or Fe remainson the substrate, which causes the occurrence of defects.

The content of each atom of Na, Ca, and Fe in the treatment liquid ismore preferably 0.01 mass ppt to 500 mass ppb and still more preferably0.05 mass ppt to 100 mass ppb.

In one aspect, the total content of the metal particles measured by asingle-particle ICP-MS (SNP-ICP-MS method) in the treatment liquidaccording to the present invention is preferably 0.001 to 100 mass pptand more preferably 1 to 100 mass ppt with respect to the total mass ofthe treatment liquid according to the present invention.

The metal atoms included in the treatment liquid for manufacturing asemiconductor as impurities are one of the factors that the occurrenceof defects in a fine pattern or a fine semiconductor element. Therefore,it has been considered that, the less the amount of metal atoms includedin the treatment liquid for manufacturing a semiconductor, the better.However, the present inventors found that the amount of metal atoms inthe treatment liquid and the rate of occurrence of defects do notnecessarily relate to each other and there is a variation in the rate ofoccurrence of defects.

However, according to the recently developed SNP-ICP-MS measurement, asthe amount of metal atoms present in a solution, the amount of ionicmetal and the amount of metal particles (nonionic metal) can bedividedly measured. Here, the metal particles (nonionic metal) refer toa metal component present in a solution as a solid without beingdissolved.

In the related art, the amount of metal atoms included in a treatmentliquid for manufacturing a semiconductor is typically analyzed using theICP-MS method or the like. In the method of the related art such as theICP-MS method, the ionic metal and the metal particles (nonionic metal)derived from the metal atoms cannot be distinguished from each other,and thus the quantity thereof is determined as the total mass of themetal atoms, that is, the total mass (hereinafter, also referred to as“total metal amount”) of the ionic metal and the particulate metal(nonionic metal).

Now that the ionic metal and the metal particles can be distinguishedfrom each other and the quantities thereof can be determined using theSNP-ICP-MS method, the present inventors conducted a thorough researchon the effect of each of the ionic metal and the metal particles(nonionic metal) derived from the metal atoms in the treatment liquid ondefects. As a result, it was found that the amount of the metalparticles (nonionic metal) has an extremely large effect on theoccurrence of defects and there is a correlation between the amount ofthe metal particles (nonionic metal) and the occurrence of defects.

In the treatment liquid according to the present invention, the totalcontent of the metal particles measured by the SNP-ICP-MS method is morepreferably 1 to 50 mass ppt.

Examples of a device that can be used for the measurement using theSNP-ICP-MS method include a device (NexION350S, manufactured byPerkinElmer Co., Ltd.) used in Examples described below, Agilent 8800triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry;manufactured by Agilent Technologies Inc.; for analyzing asemiconductor, option #200), and Agilent 8900 (manufactured by AgilentTechnologies Inc.).

In the embodiment of the present invention, a mixture of two or moretreatment liquids according to the present invention may be used as thetreatment liquid according to the present invention for variousapplications.

<Manufacturing and the like of Treatment Liquid for manufacturingSemiconductor>

The treatment liquid according to the present invention can bemanufactured using a well-known method. For example, a crude liquidincluding the compound (A) is obtained by causing raw materials to reactwith each other in the presence of a catalyst so as to synthesize thecompound (A). Next, this crude liquid is purified, for example, byfiltering and the like described below. As a result, the treatmentliquid according to the present invention can be manufactured.

The catalyst can be appropriately selected according to the compound(A). Examples of the catalyst include sulfuric acid, HgSO₄, NaNH₂,Al(C₂H₅)₃, Ipc₂BH (Diisopinocampheylborane), a solid catalyst includingcopper oxide and zinc oxide, a supported phosphoric acid catalyst, and asupported copper catalyst.

In one aspect of the method of manufacturing the treatment liquidaccording to the present invention, it is preferable that a compoundhaving at least one selected from the group consisting of Al, B, S, N,and K is used as the catalyst. In another aspect of the method ofmanufacturing the treatment liquid according to the present invention,it is preferable that a compound having at least one selected from thegroup consisting of Al, B, and S is used as the catalyst.

As the raw materials used for manufacturing the treatment liquidaccording to the present invention, raw materials purified in advance bydistillation, ion exchange, filtration, and the like are preferablyused. For example, raw materials having a purity of 99 mass % or higherand preferably 99.9 mass % or higher are preferable. It is morepreferable that high-purity raw materials are used, and it is still morepreferable that high-purity raw materials are further purified. In orderto obtain the significant effect of the present invention, it isimportant to use the high-purity raw materials.

In addition, as the catalyst used in the method of manufacturing thetreatment liquid according to the present invention, a catalyst purifiedin advance by distillation, ion exchange, filtration, and the like isalso preferably used. For example, a high-purity catalyst having apurity of 99 mass % or higher and preferably 99.9 mass % or higher ispreferable.

Next, a manufacturing device that can be suitably used for manufacturingthe treatment liquid according to the present invention will bedescribed.

[Manufacturing Device]

FIG. 1 is a schematic diagram showing an aspect of a manufacturingdevice that can be used in the method of manufacturing the treatmentliquid according to the embodiment of the present invention. Themanufacturing device 100 includes a tank 101, and the tank 101 includesa supply port 102 for supplying a cleaning liquid and/or an organicsolvent (crude liquid including the compound (A)). The manufacturingdevice 100 includes a filtration device 105, and the tank 101 and thefiltration device 105 are connected to each other through a supply pipe109 such that the fluid (for example, the cleaning liquid, the organicsolvent, and the treatment liquid) can be transferred between the tank101 and the filtration device 105. In the supply pipe 109, a valve 103and a pump 104 are disposed. In FIG. 1, the manufacturing device 100includes the tank 101 and the filtration device 105. However, themanufacturing device that can be used in the method of manufacturing thetreatment liquid according to the embodiment of the present invention isnot limited to this configuration.

In the manufacturing device 100, the fluid supplied from the supply port102 flows to the filtration device 105 through the valve 103 and thepump 104. The fluid discharged from the filtration device 105 is storedin the tank 101 through a circulation pipe 110.

The manufacturing device 100 includes a discharge unit 111 thatdischarges the treatment liquid to the circulation pipe 110. Thedischarge unit 111 includes a valve 107 and a container 108. Byswitching between the valve 106 provided in the circulation pipe and thevalve 107, the manufactured treatment liquid can be stored in thecontainer 108. In addition, a switchable pipe 113 is connected to thevalve 107 such that the cleaning liquid can be discharged to the outsideof the manufacturing device 100 through the pipe 113 after circulationcleaning. After the circulation cleaning, the cleaning liquid mayinclude particles and metal impurities and the like. According to themanufacturing device 100 including the pipe 113 from which the cleaningliquid is discharged to the outside of the manufacturing device 100, thetreatment liquid having higher defect suppressing performance can beobtained without contamination in a filling portion and the like of thecontainer 108.

Further, the manufacturing device 100 further includes a cleaning liquidmonitoring unit 112 in the circulation pipe 110. FIG. 1 shows themanufacturing device 100 that includes the cleaning liquid monitoringunit 112 in the circulation pipe 110. However, the manufacturing devicethat can be used in the method of manufacturing the treatment liquidaccording to the embodiment of the present invention is not limited tothis configuration. The cleaning liquid monitoring unit 112 may beprovided in the supply pipe 109 or may be provided in the supply pipe109 and the circulation pipe 110. In the manufacturing device 100, thecleaning liquid monitoring unit 112 may be directly provided in thecirculation pipe 110. However, the manufacturing device that can be usedin the method of manufacturing the treatment liquid according to theembodiment of the present invention is not limited to thisconfiguration. The cleaning liquid monitoring unit may be provided in afluid temporary storage tank (not shown; different from the tank 101)provided in the pipe.

FIG. 2 is a schematic diagram showing another aspect of themanufacturing device that can be used in the method of manufacturing thetreatment liquid according to the embodiment of the present invention. Amanufacturing device 200 includes the tank 101 and the filtration device105 and further includes a distillation column 201 that is connected tothe tank 101 through a pipe 202, a pipe 204, and a pipe 203 and isdisposed such that fluid can be transferred between the tank 101 and thedistillation column 201 through the pipes. In addition, themanufacturing device that can be used in the method of manufacturing thetreatment liquid according to the embodiment of the present inventiondoes not necessarily include the filtration device 105 and/or thedistillation column 201, and may further include a reaction vesselconnected to the distillation column 201 through the pipe 203.

In the manufacturing device 200, the fluid supplied to the distillationcolumn 201 through the pipe 203 is distilled in the distillation column201. The distilled fluid is stored in the tank 101 through the pipe 202.The supply pipe 109 includes the valve 103 and a valve 206. By switchingbetween the valve 103, the valve 206, and a valve 205 provided in thepipe 204, the fluid discharged from the tank 101 can be caused to flowto the filtration device 105.

In addition, in the manufacturing device 200, the fluid discharged fromthe tank 101 can be caused to flow to the distillation column 201 again.In this case, by switching between the valve 103, the valve 206, and thevalve 205, the fluid flows from the pipe 204 to the distillation column201 through the valve 207 and the pipe 203.

A material of a liquid contact portion (the definition of the liquidcontact portion will be described below) of the manufacturing device isnot particularly limited. From the viewpoint of obtaining the treatmentliquid having higher defect suppressing performance, it is preferablethat the liquid contact portion is formed of at least one selected fromthe group consisting of a nonmetallic material and an electropolishedmetallic material. In this specification, “liquid contact portion”refers to a region (for example, a tank inner surface, a liquid feedpump, a damper, a packing, an O-ring, or a pipe inner surface) that islikely to come into contact with fluid and has a thickness of 100 nmfrom the surface.

The nonmetallic material is not particularly limited and is preferably apolyethylene resin, a polypropylene resin, a polyethylene-polypropyleneresin, or a fluorine-containing resin material. From the viewpoint ofreducing the elution of metal atoms, the nonmetallic material ispreferably a fluorine-containing resin material.

As the fluorine-containing resin material, for example, a perfluororesinis used, and examples thereof include a polytetrafluoroethylene resin(PTFE), a polytetrafluoroethylene-perfluoroalkyl vinyl ether copolymer(PFA), a polytetrafluoroethylene-hexafluoropropylene copolymer resin(FEP), a polytetrafluoroethylene-ethylene copolymer resin (ETFE), apolychlorotrifluoroethylene-ethylene copolymer resin (ECTFE), avinylidene fluoride resin (PVDF), a polychlorotrifluoroethylenecopolymer resin (PCTFE), and a vinyl fluoride resin (PVF).

Preferable examples of the fluorine-containing resin material include apolytetrafluoroethylene resin, a polytetrafluoroethylene-perfluoroalkylvinyl ether copolymer, and a polytetrafluoroethylene-hexafluoropropylenecopolymer resin.

The metallic material is not particularly limited, and a well-knownmaterial can be used.

Examples of the metallic material include a metallic material in whichthe total content of chromium and nickel is higher than 25 mass % withrespect to the total mass of the metallic material. In particular, ametallic material in which the total content of chromium and nickel is30 mass % or higher with respect to the total mass of the metallicmaterial is more preferable. The upper limit value of the total contentof chromium and nickel in the metallic material is not particularlylimited and, in general, is preferably 90 mass % or lower.

Examples of the metallic material include stainless steel, carbon steel,alloy steel, nickel-chromium-molybdenum steel, chromium steel,chromium-molybdenum steel, manganese steel, and a nickel-chromium alloy.

The stainless steel is not particularly limited, and a stainless steelcan be used. An alloy including 8 mass % or higher of nickel ispreferable, and an austenite stainless steel including 8 mass % orhigher of nickel is more preferable. Examples of the austenite stainlesssteel include SUS (Steel use Stainless) 304 (Ni content: 8 mass %, Crcontent: 18 mass %), SUS304L (Ni content: 9 mass %, Cr content: 18 mass%), SUS316 (Ni content: 10 mass %, Cr content: 16 mass %), and SUS316L(Ni content: 12 mass %, Cr content: 16 mass %).

The nickel-chromium alloy is not particularly limited, and a well-knownnickel-chromium alloy can be used. In particular, a nickel-chromiumalloy in which the nickel content is 40 to 75 mass % and the chromiumcontent is 1 to 30 mass % is preferable.

Examples of the nickel-chromium alloy include HASTELLOY (trade name;hereinafter the same shall be applied), MONEL (trade name; hereinafterthe same shall be applied), and INCONEL (trade name; hereinafter thesame shall be applied). Specific examples include HASTELLOY C-276 (Nicontent: 63 mass %, Cr content: 16 mass %), HASTELLOY-C(Ni content: 60mass %, Cr content: 17 mass %), and HASTELLOY C-22 (Ni content: 61 mass%, Cr content: 22 mass %).

In addition, optionally, the nickel-chromium alloy may further includeboron, silicon, tungsten, molybdenum, copper, and cobalt in addition tothe above-described alloy.

A method of electropolishing the metallic material is not particularlylimited, and a well-known method can be used. For example, methodsdescribed in paragraphs “0011” to “0014” of JP2015-227501A andparagraphs “0036” to “0042” of JP2008-264929A can be used.

It is presumed that, by electropolishing the metallic material, thechromium content in a passive layer of the surface is higher than thatin the parent phase. Therefore, it is presumed that since metalimpurities including metal atoms in the organic solvent are not likelyto flow out from the distillation column in which the liquid contactportion is formed of the electropolished metallic material, thedistilled organic solvent in which the impurity content is reduced canbe obtained.

The metallic material may be buffed. A buffing method is notparticularly limited, and a well-known method can be used. The size ofabrasive grains used for buffing is not particularly limited and ispreferably #400 or less from the viewpoint of further reducing theroughness of the surface of the metallic material. It is preferable thatbuffing is performed before electropolishing.

From the viewpoint of obtaining the treatment liquid having higherdefect suppressing performance, it is preferable that the liquid contactportion is formed of electropolished stainless steel. In particular, ina case where the manufacturing device includes a tank, it is morepreferable that the liquid contact portion of the tank is formed ofelectropolished stainless steel. A content mass ratio (hereinafter, alsoreferred to as “Cr/Fe”) of the Cr content to the Fe content in theliquid contact portion is not particularly limited and, in general, ispreferably 0.5 to 4. In particular, from the viewpoint of furthersuppressing the elution of metal impurities and/or organic impurities inthe treatment liquid, the content mass ratio is more preferably higherthan 0.5 and lower than 3.5 and more preferably 0.7 to 3.0. In a casewhere Cr/Fe is higher than 0.5, the metal elution from the tank can besuppressed. In a case where Cr/Fe is lower than 3.5, the peeling of theliquid contact portion or the like which causes the formation ofparticles is not likely to occur.

A method of adjusting Cr/Fe in the metallic material is not particularlylimited, and examples thereof include a method of adjusting the contentof Cr atoms in the metallic material and a method of electropolishingthe metallic material such that the chromium content in a passive layerof the surface is higher than that in the parent phase.

The metallic material may be a metallic material applied to the coatingtechniques.

The coating techniques are roughly classified into three kinds: metalcoating (various kinds of plating); inorganic coating (for example,various kinds of chemical conversion coating, glass coating, concretecoating, or ceramic coating); and organic coating (rust-preventing oilcoating, paint coating, rubber coating, or plastic coating), and any oneof the coating techniques may be adopted.

Preferable examples of the coating technique include a surface treatmentusing rust-preventing oil, a rust-preventing agent, a corrosioninhibitor, a chelate compound, a strippable plastic, or a lining agent.

In particular, as the coating technique, a surface treatment using acorrosion inhibitor, a chelate compound, or a lining agent ispreferable. Here, examples of the corrosion inhibitor include variouschromates, a nitrite, a silicate, a phosphate, a carboxylic acid (forexample, oleic acid, dimer acid, or naphthenic acid), a metal soap of acarboxylic acid, a sulfonate, an amine salt, and an ester (a glycerinester or a phosphoric acid ester of higher fatty acid). Examples of thechelate compound include ethylenediaminetetraacetic acid, gluconic acid,nitrilotriacetic acid, hydroxyethyl ethylenediaminetriacetic acid, anddiethylenediaminepentaacetic acid. Examples of the lining agent includea fluororesin lining agent. A treatment using a phosphate or fluororesinlining agent is more preferable.

By the manufacturing device including the filtration device 105, thetreatment liquid having higher defect suppressing performance can beeasily obtained. A filtration member included in the filtration device105 is not particularly limited and is preferably at least one selectedfrom the group consisting of a filter having a critical particlediameter of 20 nm or less and a metal ion adsorption filter and morepreferably a metal ion adsorption filter having a critical particlediameter of 20 nm or less.

Filter Having Critical Particle Diameter of 20 nm or Less

The filter having a critical particle diameter of 20 nm or less has afunction of efficiently removing particles having a particle size of 20nm or more from the organic solvent and the like which are the rawmaterials of the treatment liquid.

The critical particle diameter of the filter is preferably 1 to 15 nmand more preferably 1 to 12 nm. In a case where the critical particlediameter is 15 nm or less, finer particles can be removed. In a casewhere the critical particle diameter is 1 nm or more, the filtrationefficiency is improved.

Here, the critical particle diameter refers to the minimum size ofparticles that can be removed by a filter. For example, in a case wherethe critical particle diameter of the filter is 20 nm, particles havinga diameter of 20 nm or more can be removed.

Examples of a material of the filter include a nylon such as 6-nylon or6,6-nylon, polyethylene, polypropylene, polystyrene, polyimide,polyamide imide, and a fluororesin. Polyimide and/or polyamide imide mayhave at least one selected from the group consisting of a carboxy group,a salt type carboxy group, and an —NH— bond. From the viewpoint ofsolvent resistance, a fluororesin or polyimide and/or polyamide imide ispreferable. In addition, from the viewpoint of adsorbing metal ions, anylon such as 6-nylon or 6,6-nylon is more preferable.

The filtration device 105 may include a plurality of filters. In a casewhere the filtration device 105 includes a plurality of filters, anotherfilter is not particularly limited and is preferably a filter having acritical particle diameter of 50 nm or more (for example, a microfiltermembrane for removing fine particles having a pore size of 50 nm ormore). In a case where fine particles are present in a material to bepurified in addition to the colloidal impurities, in particular,including metal atoms such as iron or aluminum, the material to bepurified is filtered using a filter having a critical particle diameterof 50 nm or more (for example, a microfilter membrane for removing fineparticles having a pore size of 50 nm or more) before being filteredusing a filter having a critical particle diameter of 20 nm or less (forexample, a microfilter membrane for removing fine particles having apore size of 20 nm or less). As a result, the filtration efficiency ofthe filter having a critical particle diameter of 20 nm or less (forexample, a microfilter membrane for removing fine particles having apore size of 20 nm or less) is improved, and the performance of removingparticles is further improved.

Metal Ion Adsorption Filter

It is preferable that the filtration device 105 includes the metal ionadsorption filter.

The metal ion adsorption filter is not particularly limited and, forexample, a well-known metal ion adsorption filter can be used.

In particular, an ion exchangeable filter is preferable as the metal ionadsorption filter. Here, metal ions as an adsorption target are notparticularly limited. From the viewpoint of causing defects of asemiconductor device to occur, metal ions including one selected fromFe, Cr, Ni, and Pb are preferable, and ions of metals including each ofFe, Cr, Ni, and Pb are more preferable.

From the viewpoint of improving the adsorption performance of the metalions, it is preferable that the metal ion adsorption filter has an acidgroup on the surface. Examples of the acid group include a sulfo groupand a carboxy group.

Examples of a substrate (material) forming the metal ion adsorptionfilter include cellulose, diatom earth, nylon, polyethylene,polypropylene, polystyrene, and a fluororesin. From the viewpoint ofimproving the adsorption efficiency of the metal ions, nylon is morepreferable.

In addition, the metal ion adsorption filter may be formed of a materialincluding polyimide and/or polyamide imide. Examples of the metal ionadsorption filter include polyimide and/or polyamide imide porousmembrane described in JP2016-155121A.

The polyimide and/or polyamide imide porous membrane may have at leastone selected from the group consisting of a carboxy group, a salt typecarboxy group, and an —NH— bond. In a case where the metal ionadsorption filter is formed of a fluororesin, polyimide, and/orpolyamide imide, higher solvent resistance can be obtained.

Organic Impurity Adsorption Filter

The filtration device 105 may further include an organic impurityadsorption filter.

The organic impurity adsorption filter is not particularly limited and,for example, a well-known organic impurity adsorption filter can beused.

In particular, from the viewpoint of improving the adsorptionperformance organic impurities, it is preferable that the organicimpurity adsorption filter has an organic skeleton that is interactivewith organic impurities on the surface (in other words, the surface ismodified with an organic skeleton that is interactive with organicimpurities). Examples of the organic skeleton that is interactive withorganic impurities include a chemical structure that reacts with organicimpurities such that the organic impurities can be trapped in theorganic impurity adsorption filter. More specifically, in a case wherean n-long chain alkyl alcohol (for example, a structural isomer in acase where 1-long chain alkyl alcohol is used as the organic solvent) isincluded as an organic impurity, examples of the organic skeletoninclude an alkyl group. In addition, in a case where a dibutyl hydroxytoluene (BHT) is included as an organic impurity, examples of theorganic skeleton include a phenyl group.

Examples of a substrate (material) forming the organic impurityadsorption filter include cellulose on which activated carbon issupported, diatom earth, nylon, polyethylene, polypropylene,polystyrene, and a fluororesin.

In addition, as the organic impurity adsorption filter, a filter inwhich activated carbon adheres to non-woven fabric described inJP2002-273123A and JP2013-150979A can also be used.

The organic impurity adsorption filter is also applicable to a physicaladsorption method as well as the above-described chemical adsorption(adsorption using the organic impurity adsorption filter having anorganic skeleton that is interactive with organic impurities on thesurface).

For example, in a case where BHT is included in as an organic impurity,the structure of BHT is larger than 10 ongstrom (=1 nm). Therefore, byusing an organic impurity adsorption filter having a pore size of 1 nm,BHT cannot pass through the pore of the filter. That is, BHT isphysically trapped in the filter, and thus is removed from the materialto be purified. This way, the organic impurities can also be removed byusing the physical removal method as well as the chemical interaction.However, in this case, a filter having a pore size of 3 nm or more isused as the “particle removal filter”, and a filter having a pore sizeof less than 3 nm is used as the organic impurity adsorption filter.

As described above, a combination of different filters may be used. Atthis time, the filtering using a first filter may be performed once, ortwice or more. In a case where filtering is performed two or more timesusing different filters in combination, the filters may be the same asor different from each other but are preferably different from eachother. Typically, it is preferable that a first filter and a secondfilter are different from each other in at least one of a pore size or aforming material.

It is preferable that the pore size of the filter used for the second orsubsequent filtering is equal to or less than that of the filter usedfor the first filtering. In addition, a combination of first filtershaving different pore sizes in the above-described range may be used.Here, the pore size of the filter can refer to a nominal value of amanufacturer of the filter. A commercially available filter can beselected from various filters manufactured by Pall Corporation, ToyoRoshi Kaisha, Ltd., Entegris Japan Co., Ltd. (former MykrolisCorporation), or Kits Microfilter Corporation. In addition, “P-NylonFilter (formed of polyamide, pore size: 0.02 μm, critical surfacetension: 77 mN/m)” (manufactured by Pall Corporation), “PE Clean Filter(formed of high-density polyethylene, pore size: 0.02 μm)” (manufacturedby Pall Corporation), or “PE Clean Filter (formed of high-densitypolyethylene, pore size: 0.01 μm)” (manufactured by Pall Corporation)can also be used.

The method of manufacturing the treatment liquid according to theembodiment of the present invention may include a step of cleaning themanufacturing device using the cleaning liquid. In this method, thecleaning liquid is supplied from the supply port 102 of the tank 101.The supply amount of the cleaning liquid is not particularly limited andis preferably adjusted such that the liquid contact portion of the tank101 can be sufficiently cleaned. The volume of the cleaning liquidsupplied is preferably 30 vol % or higher with respect to the volume ofthe tank 101. In a case where the cleaning liquid is supplied from thesupply port 102, the valve 103 may be closed or opened. However, fromthe viewpoint of more easily cleaning the tank 101, in a case where thecleaning liquid is supplied from the supply port 102, it is preferablethat the valve 103 is closed.

The cleaning liquid supplied to the tank 101 may be transferredimmediately into the manufacturing device, or may be transferred intothe manufacturing device (for example, through the supply pipe 109)after cleaning the inside of the tank 101. A method of cleaning theinside of the tank 101 using the cleaning liquid is not particularlylimited, and examples thereof include a method of cleaning the inside ofthe tank 101 by rotating stirring blades (not shown) included in thetank 101. The time during which the tank is cleaned using the cleaningliquid is not particularly limited and may be appropriately selectedaccording to the material of the liquid contact portion of the tank 101,the kind of the treatment liquid to be manufactured, the possibility ofcontamination, and the like. In general, the time is preferably about0.1 seconds to 48 hours. In a case where only the tank 101 is cleaned,the cleaning liquid after cleaning may be discharged from, for example,a discharge port (not shown) provided in the tank bottom portion.

A method of cleaning the supply pipe 109 and the like of themanufacturing device 100 using the cleaning liquid is not particularlylimited, and a method (hereinafter, also referred to as “circulationcleaning”) of circulating the cleaning liquid in the manufacturingdevice through the supply pipe 109 and the circulation pipe 110 byoperating the pump 104 in a state where the valve 103 and the valve 106are opened and the valve 107 is closed is preferable. With theabove-described method, while transferring the cleaning liquid, foreignmatters and the like attached to the liquid contact portions of the tank101, the filtration device 105, the supply pipe 109, and the like can beefficiently dispersed and/or can be efficiently dissolved using thecleaning liquid.

In particular, in a case where the manufacturing device includes thefiltration device, the circulation cleaning is more preferable as thecleaning method. An example of the circulation cleaning will bedescribed using FIG. 1. First, the cleaning liquid supplied from thetank 101 into the manufacturing device through the valve 103 returns(circulates) to the tank 101 again through the supply pipe 109 (throughthe filtration device 105, the circulation pipe 110, and the valve 106).At this time, the cleaning liquid is filtered through the filtrationdevice 105 such that particles and the like dissolved and dispersed inthe cleaning liquid are removed and the cleaning effect can be furtherimproved.

In another aspect of the cleaning method, for example, another methodmay be used, the method including: causing the cleaning liquid suppliedfrom the supply port 102 of the tank 101 into the manufacturing deviceto flow into the filtration device 105 through the valve 103 and thepump 104 by operating the pump 104 in a state where the valve 103 andthe valve 107 are opened and the valve 106 is closed; and dischargingthe cleaning liquid to the outside of the manufacturing device throughthe valve 107 without being circulated (in this specification,hereinafter, this method will also be referred to as “batch cleaning”).In this case, as described above, the cleaning liquid may be suppliedintermittently into the manufacturing device in a predetermined amount,or may be supplied continuously into the manufacturing device.

(Cleaning Liquid)

The cleaning liquid used for performing cleaning in advance as describedabove is not particularly limited, and a well-known cleaning liquid canbe used.

Examples of the cleaning liquid include water, alkylene glycol monoalkylether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkylalkoxy propionate, a cyclic lactone (preferably having 4 to 10 carbonatoms), a monoketone compound (preferably having 4 to 10 carbon atoms)which may include a ring, alkylene carbonate, alkyl alkoxy acetate, andalkyl pyruvate.

In addition, as the cleaning liquid, for example, cleaning liquidsdescribed in JP2016-57614A, JP2014-219664A, JP2016-138219A, andJP2015-135379A may be used.

It is preferable that the cleaning liquid includes at least one selectedfrom the group consisting of propylene glycol monomethyl ether (PGME),cyclopentanone (CyPe), butyl acetate (nBA), propylene glycol monomethylether acetate (PGMEA), cyclohexanone (CyHx), ethyl lactate (EL), methyl2-hydroxyisobutyrate (HBM), cyclopentanone dimethylacetal (DBCPN),γ-butyrolactone (GBL), dimethyl sulfoxide (DMSO), ethylene carbonate(EC), propylene carbonate (PC), 1-methyl-2-pyrrolidone (NMP), isoamylacetate (iAA), isopropanol (IPA), methyl ethyl ketone (MEK), and4-methyl-2-pentanol (MIBC) is preferable, it is more preferable thecleaning liquid includes at least one selected from the group consistingof PGMEA, NMP, PGME, nBA, PC, CyHx, GBL, MIBC, EL, DMSO, iAA, MEK, PC,and CyPe, and it is still more preferable the cleaning liquid is formedof at least one selected from the group consisting of PGMEA, NMP, PGME,nBA, PC, CyHx, GBL, MIBC, EL, DMSO, iAA, MEK, PC, and CyPe.

As the cleaning liquid, one kind may be used alone, or two or more kindsmay be used in combination. In addition, the treatment liquid accordingto the present invention may be used as the cleaning liquid.

[Method of Adjusting Metal Content]

In the treatment liquid according to the present invention, the ionconcentration of each of Cr, Co, Cu, Pb, Li, Mg, Mn, Ni, K, Ag, Zn, andthe like is preferably 1 ppm (parts per million) or lower and morepreferably 1 ppb or lower. In particular, it is more preferable that theion concentration is in the order of ppt (all the concentrations arebased on mass), and it is still more preferable that the treatmentliquid does not substantially include Cr, Co, Cu, Pb, Li, Mg, Mn, Ni, K,Ag, Zn, and the like.

The metal content of the treatment liquid according to the presentinvention may be adjusted by repeating distillation, filter filtration,filtration using an ion exchange resin, adsorption purification, or thelike to sufficiently purify the treatment liquid, for example, at leastone of a step of preparing the respective raw materials used formanufacturing the treatment liquid or a step after the preparation ofthe treatment liquid.

Here, the method of adjusting the metal content (hereinafter, alsoreferred to as “method of reducing the metal concentration”) is notparticularly limited, and examples thereof include adsorptionpurification using silicon carbide described in WO2012/043496A. Further,an example of using the adsorption purification in combination withdistillation, filter filtration, or filtration using an ion exchangeresin to sufficiently purify the treatment liquid is also preferable.

From the viewpoint of obtaining the effects of the present invention, itis more preferable that the method of adjusting the metal content isperformed in the step of preparing the respective raw materials used formanufacturing the treatment liquid. In addition, in the raw materials,it is preferable that the content of the specific metal atoms accordingto the present invention or the content of an inorganic ion such as asulfate ion, a chloride ion, or a nitrate ion and a metal ion describedbelow are reduced.

In another method relating to the method of reducing the metalconcentration, for example, as “container” that stores the raw materialsused for manufacturing the treatment liquid, a container in which theelution of impurities is reduced as described below regarding a storagecontainer that stores the treatment liquid according to the presentinvention. In addition, for example, a method of lining an inner wall ofthe pipe with a fluororesin to prevent the specific metal atoms frombeing eluted from “the pipe” or the like used for the preparation of thetreatment liquid can also be used.

[Impurities and Coarse Particles]

In addition, it is preferable that the treatment liquid according to thepresent invention does not substantially include coarse particles.

Here, the coarse particles included in the treatment liquid refer toparticles of dirt, dust, an organic solid matter, an inorganic solidmatter, or the like included in raw materials as impurities or particlesof dirt, dust, an organic solid matter, an inorganic solid matter, orthe like introduced as contaminant during the preparation of thetreatment liquid. The coarse particles correspond to particles thatfinally remain in the treatment liquid without being dissolved. Theamount of the coarse particles present in the treatment liquid can bemeasured in a liquid phase using a commercially available measuringdevice according to a light scattering particle measurement method inliquid in which a laser is used as a light source.

[Kit and Concentrated Liquid]

The treatment liquid according to the present invention may be used as akit by separately adding other raw materials thereto. In this case, asthe other raw materials that are separately added for use, not only asolvent such as water or an organic solvent but also other compounds maybe mixed with each other for use according to the intended use. From theviewpoint of significantly obtaining the effects of the presentinvention, in a case where the content of Na, Ca, or Fe in the solventthat can be used at this time is in the above-described specific valuerange of the present invention, the desired effects of the presentinvention can be significantly obtained.

<Container>

The treatment liquid according to the present invention can be filledinto any container (irrespective of whether or not it is theabove-described kit) to be stored, transported, and used unless it has aproblem such as corrosiveness. As the container, a container for asemiconductor in which the cleanliness is high and the elution ofimpurities is reduced is preferable. Examples of the container to beused include “Green Bottle” series (manufactured by Alcello ChemicalCo., Ltd.) and “Pure Bottle” (manufactured by Kodama Plastics Co.,Ltd.). However, the present invention is not limited to the examples.

It is preferable that a liquid contact portion of the container isformed of a nonmetallic material or stainless steel.

Examples of the nonmetallic material include the materials describedabove as the examples of the nonmetallic material used for the liquidcontact portion of the distillation column. In particular, in a casewhere the container having a liquid contact portion formed of afluororesin is used, the occurrence of problems such as the elution ofethylene, propylene, or an oligomer can be suppressed as compared to acase where a container having a liquid contact portion formed of apolyethylene resin, a polypropylene resin, or apolyethylene-polypropylene resin is used.

Specific examples of the container having a liquid contact portionformed of a fluororesin include a Fluoro Pure PFA composite drum(manufactured by Entegris, Inc.). In addition, for example, containersdescribed in page 4 and the like of JP1991-502677A (JP-H3-502677A), page3 and the like of WO2004/016526A, and pages 9 and 16 and the like ofWO1999/46309A can be used. In a case where the liquid contact portion isformed of the nonmetallic material, it is preferable that the elutioninto the nonmetallic material is suppressed.

The liquid contact portion of the container in contact with thetreatment liquid is formed of preferably stainless steel and morepreferably electropolished stainless steel.

In a case where the treatment liquid is stored in the container, theelution of impurity metal and/or organic impurities in the treatmentliquid stored in the container is further suppressed.

The form of the stainless steel is as described above regarding thematerial of the liquid contact portion of the distillation column. Inaddition, the same shall be applied to the electropolished stainlesssteel.

The Cr/Fe ratio in the stainless steel forming the liquid contactportion of the container is as described above regarding the Cr/Fe ratioin the liquid contact portion of the tank.

It is preferable that the inside of these containers is cleaned beforefilling. In addition, the liquid used for cleaning is not particularlylimited, and the metal content in the liquid is preferably lower than0.001 mass ppt (parts per trillion). In addition, in a case where theliquid used for cleaning is water described below or another organicsolvent that is purified such that the metal content in theabove-described range, the treatment liquid according to the presentinvention, a diluted solution of the treatment liquid according to thepresent invention, or a liquid including at least one compound added tothe treatment liquid according to the present invention, the desiredeffects of the present invention can be significantly obtained.

The treatment liquid may be bottled in a container such as a gallonbottle or a coated bottle to be transported or stored. The gallon bottlemay be formed of a glass material or other materials.

In order to prevent a change in the component of the solution duringstorage, the inside of the container may be replaced with inert gas (forexample, nitrogen or argon) having a purity of 99.99995 vol %. Inparticular, gas having a low moisture content is preferable. Inaddition, the temperature during transport or storage may be normaltemperature or may be controlled to be in a range of −20° C. to 30° C.in order to prevent deterioration.

In addition, it is preferable that foreign matter attached to a lid ofone of various containers is removed by cleaning the lid with an acid oran organic solvent before cleaning the container because infiltration offoreign matters from the lid can be prevented.

[Water]

As the water used regarding the present invention, for example, waterthat can be used in a manufacturing step of the treatment liquidaccording to the present invention, water that can be used in a patternforming step according to the present invention, water that can be usedfor cleaning the storage container of the treatment liquid according tothe present invention, or water that can be used in measurement of thecomponents of the treatment liquid according to the present invention orin measurement for evaluating defect suppressing performance andlithographic performance relating to the effects of the presentinvention, ultrapure water for manufacturing a semiconductor ispreferably used. In addition, it is more preferable that water obtainedby further purifying the ultrapure water such that inorganic anions,metal ions, and the like are reduced is used. The purification method isnot particularly limited, and purification using a filtration film or anion-exchange membrane or purification using distillation is preferable.In addition, for example, it is preferable that the purification isperformed using a method described in JP2007-254168A.

In addition, in one aspect, the metal content in the water is preferablylower than 0.001 mass ppt (parts per trillion).

[Clean Room]

It is preferable that all the handling operations including theadjustment of the treatment liquid according to the present invention,the unsealing and/or cleaning of the storage container, and the fillingof the treatment liquid, the treatment analysis, and the measurement areperformed in a clean room. It is preferable that the clean roomsatisfies the clean room standards 14644-1. It is preferable that theclean room satisfies any one of ISO Class 1, ISO Class 2, ISO Class 3,and ISO Class 4, it is more preferable that the clean room satisfies ISOClass 1 or ISO Class 2, and it is still more preferable that the cleanroom satisfies ISO Class 1.

[Use of Treatment Liquid]

The treatment liquid according to the present invention is preferablyused for manufacturing a semiconductor. Specifically, in manufacturingsteps of a semiconductor device including a lithography step, an etchingstep, an ion implantation step, and a peeling step, the treatment liquidis used for treating an organic matter after the end of each step orbefore the start of the next step, and specifically is suitably used asa pre-wet liquid, a developer, a rinsing liquid, a peeling liquid, orthe like. For example, the treatment liquid can also be used for rinsingan edge line of a semiconductor substrate before and after resistapplication.

In addition, the treatment liquid can also be used as a cleaning liquidof a device for manufacturing various treatment liquids that are usedfor manufacturing a semiconductor.

In addition, the treatment liquid can also be used as a dilute solutionof a resin included in a resist solution (described below). That is, thetreatment liquid can also be used as the solvent included in the actinicray-sensitive or radiation-sensitive composition.

In addition, the treatment liquid can also be suitably used for otherapplications other than the manufacturing of a semiconductor, and can beused, for example, as a developer such as polyimide, a resist for asensor, or a resist for a lens, or a rinsing liquid.

In addition, the treatment liquid can also be used for medicalapplications or as a solvent for cleaning. In particular, the treatmentliquid can be suitably used for cleaning a container, a pipe, asubstrate (for example, a wafer or glass), or the like.

<Pattern Forming Method>

Basically, in a method of manufacturing a semiconductor device, thetreatment liquid according to the present invention is a treatmentliquid used as a developer, a rinsing liquid, a pre-wet liquid, peelingliquid, or the like. In one aspect, in a pattern forming method includedin the method of manufacturing a semiconductor device, it is preferablethat the treatment liquid is used as a developer, a rinsing liquid, or apre-wet liquid.

The pattern forming method according to the present invention includes:a resist film forming step of applying an actinic ray-sensitive orradiation-sensitive composition (hereinafter, also referred to as“resist composition”) to a substrate to form an actinic ray-sensitive orradiation-sensitive film (hereinafter, also referred to as “resistfilm”); an exposure step of exposing the resist film; and a treatmentstep of treating the substrate to which the resist composition isapplied or the exposed resist film using the above-described treatmentliquid.

In the pattern forming method according to the present invention, thetreatment liquid according to the present invention may be used as anyone of a developer, a rinsing liquid, and a pre-wet liquid, ispreferably used as two of a developer, a rinsing liquid, and a pre-wetliquid and is more preferably used as a developer, a rinsing liquid, anda pre-wet liquid.

Hereinafter, each of the steps included in the pattern forming methodaccording to the present invention will be described. In addition, as anexample of the treatment step using the treatment liquid according tothe present invention, each of a pre-wet step, a development step, and arinsing step will be described.

<Pre-Wet Step>

In order to improve coating properties, the pattern forming methodaccording to the present invention may include a pre-wet step ofapplying a pre-wet liquid to the substrate in advance before the step offorming the resist film using the actinic ray-sensitive orradiation-sensitive composition. For example, the pre-wet step isdescribed in JP2014-220301A, the content of which is incorporated hereinby reference.

<Resist Film Forming Step>

The resist film forming step is a step of forming a resist film using anactinic ray-sensitive or radiation-sensitive composition and, forexample, can be performed using the following method.

In order to form the resist film (actinic ray-sensitive orradiation-sensitive composition film) on the substrate using the actinicray-sensitive or radiation-sensitive composition, respective componentsdescribed below are dissolved in a solvent to prepare an actinicray-sensitive or radiation-sensitive composition, the actinicray-sensitive or radiation-sensitive composition is optionally filteredthrough a filter and applied to the substrate. As the filter, a filterformed of polytetrafluoroethylene, polyethylene, or nylon and having apore size of preferably 0.1 μm or less, more preferably 0.05 μm or less,and still more preferably 0.03 μm or less is preferable.

The actinic ray-sensitive or radiation-sensitive composition is appliedto the substrate (for example, silicon or a silicon dioxide coating),which is used for manufacturing an integrated circuit element, using anappropriate coating method such as a method using a spinner. Next, theactinic ray-sensitive or radiation-sensitive composition is dried toform a resist film. Optionally, various underlayer films (an inorganicfilm, an organic film, or an antireflection film) may be formed belowthe resist film.

As the drying method, a method of drying heating the composition isgenerally used. Heating may be performed using means provided in atypical exposure or developing device, and may be performed using a hotplate or the like.

The heating temperature is preferably 80° C. to 180° C., more preferably80° C. to 150° C., still more preferably 80° C. to 140° C., and evenstill more preferably 80° C. to 130° C. The heating time is preferably30 to 1000 seconds, more preferably 60 to 800 seconds, and still morepreferably 60 to 600 seconds.

The thickness of the resist film is generally 200 nm or less andpreferably 100 nm or less.

For example, in order to resolve a 1:1 line-and-space pattern having asize of 30 nm or less, the thickness of a resist film to be formed ispreferably 50 nm or less. In a case where a resist film having athickness of 50 nm or less is applied to a development step describedbelow, pattern collapse is not likely to occur, and higher resolutionperformance can be obtained.

The thickness is more preferably in a range of 15 nm to 45 nm. In a casewhere the thickness is 15 nm or more, sufficient etching resistance canbe obtained. The thickness is still more preferably is in a range of 15nm to 40 nm. In a case where the thickness is in the above-describedrange, etching resistance and higher resolution performance can besimultaneously satisfied.

In the pattern forming method according to the present invention, anupper layer film (top coat film) may be formed over the resist film. Theupper layer film can be formed using, for example, an upper layerfilm-forming composition including a hydrophobic resin, an acidgenerator, and a basic compound The upper layer film and the upper layerfilm-forming composition will be described below.

<Exposure Step>

The exposure step is a step of exposing the resist film and, forexample, can be performed using the following method.

The resist film formed as described above is irradiated with an actinicray or radiation through a predetermined mask. For irradiation of anelectron beam, drawing (direct drawing) not using a mask is generallyused.

The actinic ray or radiation is not particularly limited, and examplesthereof include KrF excimer laser light, ArF excimer laser light,extreme ultraviolet (EUV) light, and an electron beam (EB). The exposuremay be immersion exposure.

<Baking>

In the pattern forming method according to the present invention, it ispreferable that baking (heating) is performed before development afterexposure. Due to the baking, a reaction of an exposed portion ispromoted, and sensitivity and a pattern shape are further improved.

The heating temperature is preferably 80° C. to 150° C., more preferably80° C. to 140° C., and still more preferably 80° C. to 130° C.

The heating time is preferably 30 to 1000 seconds, more preferably 60 to800 seconds, and still more preferably 60 to 600 seconds.

Heating may be performed using means provided in a typical exposure ordeveloping device, and may be performed using a hot plate or the like.

<Development Step>

The development step is a step of developing the exposed resist filmwith the developer.

Examples of the developing method include: a method (dipping method) ofdipping the substrate in a container filled with the developer for agiven period of time; a method (puddle method) of causing the developerto accumulate on a surface of the substrate with a surface tension andmaintaining this state for a given period of time for development; amethod (spraying method) of spraying the developer to a surface of thesubstrate; and a method (dynamic dispense method) of continuouslyjetting the developer to the substrate, which is rotating at a givenspeed, while scanning a developer jetting nozzle on the substrate at agiven speed.

In addition, a step of stopping development while replacing the solventwith another solvent may be performed after the development step.

The developing time is not particularly limited as long as it is aperiod of time where a non-exposed portion of a resin is sufficientlydissolved. The development time is typically 10 to 300 seconds andpreferably 20 to 120 seconds.

The temperature of the developer is preferably 0° C. to 50° C. and morepreferably 15° C. to 35° C.

As the developer used in the development step, the above-describedtreatment liquid is preferably used. The developer is as describedabove. In addition to the development using the treatment liquid,development using an alkali developer may be further performed(so-called double development).

<Rinsing Step>

The rinsing step is a step of performing rinsing with the rinsing liquidafter the development step.

In the rinsing step, a developed wafer is rinsed with theabove-described rinsing liquid.

A rinsing method is not particularly limited, and examples thereofinclude: a method (rotation jetting method) of continuously jetting therinsing liquid to the substrate which is rotating at a given speed; amethod (dipping method) of dipping the substrate in a container filledwith the rinsing liquid for a given period of time; and a method(spraying method) of spraying the rinsing liquid to a surface of thesubstrate. In particular, it is preferable that the rinsing step isperformed using the rotation jetting method such that the rinsedsubstrate is rotated at a rotation speed of 2000 rpm to 4000 rpm toremove the rinsing liquid from the substrate.

The rinsing time is not particularly limited and is typically 10 secondsto 300 seconds. The rising time is preferably 10 seconds to 180 secondsand most preferably 20 seconds to 120 seconds.

The temperature of the rinsing liquid is preferably 0° C. to 50° C. andmore preferably 15° C. to 35° C.

In addition, after the development or the rising, a treatment ofremoving the developer or the rinsing liquid, which is attached to thepattern, with supercritical fluid may be performed.

Further, after the development, the rinsing, or the treatment using thesupercritical fluid, heating may be performed to remove the solventremaining in the pattern. The heating temperature is not particularlylimited as long as an excellent resist pattern can be obtained, and istypically 40° C. to 160° C. The heating temperature is preferably 50° C.to 150° C. and most preferably 50° C. to 110° C. The heating time is notparticularly limited as long as an excellent resist pattern can beobtained, and is typically 15 to 300 seconds and preferably 15 to 180seconds.

As the rinsing liquid, the above-described treatment liquid ispreferably used. The description of the rinsing liquid is as describedabove.

As described above, in the pattern forming method according to thepresent invention, any one of a developer, a rinsing liquid, and apre-wet liquid may be the above-described treatment liquid according tothe present invention, any two of a developer, a rinsing liquid, and apre-wet liquid may be the above-described treatment liquid according tothe present invention, and all the three of a developer, a rinsingliquid, and a pre-wet liquid may be the above-described treatment liquidaccording to the present invention.

In one aspect, it is preferable that the treatment liquid and theactinic ray-sensitive or radiation-sensitive resin composition used inthe pattern forming method according to the present invention satisfythe following relationship.

That is, it is preferable that the actinic ray-sensitive orradiation-sensitive resin composition and the treatment liquid accordingto the present invention are used so as to satisfy a relationship inwhich a dissolution rate of the actinic ray-sensitive orradiation-sensitive film, which is formed using the actinicray-sensitive or radiation-sensitive resin composition, in the treatmentliquid according to the present invention is 0.0016 to 0.33 nm/sec.

Here, the dissolution rate of the actinic ray-sensitive orradiation-sensitive film in the treatment liquid according to thepresent invention is a rate at which the film thickness is reduced whenthe actinic ray-sensitive or radiation-sensitive film is formed and thenis dipped in the treatment liquid according to the present invention. Inthe present invention, the dissolution rate refers to a dissolution rateat 23° C. This dissolution rate is more preferably 0.0016 to 0.16 nm/secand still more preferably 0.0016 to 0.08 nm/sec.

<Actinic Ray-Sensitive or Radiation-Sensitive Composition (ResistComposition)>

Next, the actinic ray-sensitive or radiation-sensitive composition whichis preferably used in combination with the treatment liquid according tothe present invention will be described in detail.

(A) Resin

It is preferable that a resin (A) is included as the actinicray-sensitive or radiation-sensitive composition which is preferablyused in combination with the treatment liquid according to the presentinvention. The resin (A) includes at least (i) a repeating unit having agroup which is decomposed by the action of an acid to produce a carboxylgroup (may further include a repeating unit having a phenolic hydroxylgroup), or includes may at least (ii) a repeating unit having a phenolichydroxyl group.

In a case where the resin (A) includes the repeating unit having a groupwhich is decomposed by the action of an acid to produce a carboxylgroup, the solubility in an alkali developer increases and thesolubility in the organic solvent increases due to the action of anacid.

Examples of the repeating unit having a phenolic hydroxyl group includedin the resin (A) include a repeating unit represented by the followingFormula (I).

In the formula,

R₄₁, R₄₂, and R₄₃ each independently represent a hydrogen atom, an alkylgroup, a halogen atom, a cyano group, or an alkoxycarbonyl group. R₄₂may be bonded to Ar₄ to form a ring. In this case, R₄₂ represents asingle bond or an alkylene group.

X₄ represents a single bond, —COO—, or —CONR₆₄—, and R₆₄ represents ahydrogen atom or an alkyl group.

L₄ represents a single bond or an alkylene group.

Ar₄ represents a (n+1)-valent aromatic ring group, and in a case whereAr₄ is bonded to R₄₂ to form a ring, Ar₄ represents a (n+2)-valentaromatic ring group.

n represents an integer of 1 to 5.

As the alkyl group represented by R₄₁, R₄₂, and R₄₃ in Formula (I), analkyl group having 20 or less carbon atoms which may have a substituentsuch as a methyl group, an ethyl group, a propyl group, an isopropylgroup, a n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexylgroup, an octyl group, or a dodecyl group is preferable, an alkyl grouphaving 8 or less carbon atoms is more preferable, and an alkyl grouphaving 3 or less carbon atoms is still more preferable.

In Formula (I), the cycloalkyl group represented by R₄₁, R₄₂, and R₄₃may be monocyclic or polycyclic. In particular, a monocycloalkyl grouphaving 3 to 8 carbon atoms which may have a substituent such as acyclopropyl group, a cyclopentyl group, or a cyclohexyl group ispreferable.

Examples of the halogen atom represented by R₄₁, R₄₂, and R₄₃ in Formula(I) include a fluorine atom, a chlorine atom, a bromine atom, and aniodine atom. In particular, a fluorine atom is preferable.

As the alkyl group included in the alkoxycarbonyl group represented byR₄₁, R₄₂, and R₄₃ in Formula (I), the same alkyl groups as describedabove regarding R₄₁, R₄₂, and R₄₃ are preferable.

Preferable examples of a substituent of each of the groups include analkyl group, a cycloalkyl group, an aryl group, an amino group, an amidogroup, an ureido group, a urethane group, a hydroxyl group, a carboxylgroup, a halogen atom, an alkoxy group, a thioether group, an acylgroup, an acyloxy group, an alkoxycarbonyl group, a cyano group, and anitro group. The number of carbon atoms in the substituent is preferably8 or less.

Ar₄ represents an (n+1)-valent aromatic ring group. In a case where nrepresents 1, a divalent aromatic ring group may have a substituent, andpreferable examples thereof include an arylene group having 6 to 18carbon atoms such as a phenylene group, a tolylene group, a naphthylenegroup, or an anthracenylene group; and an aromatic ring group having aheterocycle such as thiophene, furan, pyrrole, benzothiophene,benzofuran, benzopyrrole, triazine, imidazole, benzoimidazole, triazole,thiadiazole, or thiazole.

In a case where n represents an integer of 2 or more, preferablespecific examples of the (n+1)-valent aromatic ring group include groupsobtained by removing arbitrary (n-1) hydrogen atoms from the specificexamples of the above-described divalent aromatic ring groups.

The (n+1)-valent aromatic ring group may further have a substituent.

Examples of a substituent which may be included in the alkyl group, thecycloalkyl group, the alkoxycarbonyl group, the alkylene group, and the(n+1)-valent aromatic ring group include: the alkoxy groups representedby R₄₁, R₄₂, and R₄₃ in Formula (I), such as an alkyl group, a methoxygroup, an ethoxy group, a hydroxyethoxy group, a propoxy group, ahydroxypropoxy group, or a butoxy group; and an aryl group such as aphenyl group.

As an alkyl group represented by R₆₄ in —CONR₆₄— (R₆₄ represents ahydrogen atom or an alkyl group) represented by X₄, an alkyl grouphaving 20 or less carbon atoms which may have a substituent such as amethyl group, an ethyl group, a propyl group, an isopropyl group, an-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group,an octyl group, or a dodecyl group is preferable, and an alkyl grouphaving 8 or less carbon atoms is more preferable. As X₄, a single bond,—COO—, or —CONH— is preferable, and a single bond or —COO— is morepreferable.

Preferable examples of the alkylene group represented by L₄ include analkylene group having 1 to 8 carbon atoms which may have a substituentsuch as a methylene group, an ethylene group, a propylene group, abutylene group, a hexylene group, or an octylene group.

As Ar₄, an aromatic ring group having 6 to 18 carbon atoms which mayhave a substituent is more preferable, and a benzene ring group, anaphthalene ring group, or a biphenylene ring group is still morepreferable.

It is preferable that the repeating unit represented by Formula (I)includes a hydroxystyrene structure. That is, it is preferable that Ar₄represents a benzene ring group.

Preferable examples of the repeating unit having a phenolic hydroxylgroup included in the resin (A) include a repeating unit represented bythe following Formula (p1).

In Formula (p1), R represents a hydrogen atom or a linear or branchedalkyl group having a halogen atom or 1 to 4 carbon atoms. A plurality ofR's may be the same as or different from each other. As R in Formula(p1), a hydrogen atom is preferable.

Ar in Formula (p1) represents an aromatic ring, and examples thereofinclude: an aromatic hydrocarbon ring having 6 to 18 carbon atoms whichmay have a substituent such as a benzene ring, a naphthalene ring, ananthracene ring, a fluorene ring, or a phenanthrene ring; and anaromatic heterocycle having a heterocycle such as a thiophene ring, afuran ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, abenzopyrrole ring, a triazine ring, an imidazole ring, a benzoimidazolering, a triazole ring, a thiadiazole ring, or a thiazole ring. Amongthese, a benzene ring is most preferable.

In Formula (p1), m represents an integer of 1 to 5 and preferably 1.

Hereinafter, specific examples of the repeating unit having a phenolichydroxyl group included in the resin (A) will be shown, but the presentinvention is not limited thereto. In the formulae, a represents 1 or 2.

The content of the repeating unit having a phenolic hydroxyl group ispreferably 0 to 50 mol %, more preferably 0 to 45 mol %, and still morepreferably 0 to 40 mol % with respect to all the repeating units of theresin (A).

The repeating unit having a group which is decomposed by the action ofan acid to produce a carboxyl group included in the resin (A) is arepeating unit having a group which is substituted with a group obtainedby a hydrogen atom being removed from a carboxyl group due todecomposition caused by the action of an acid.

Examples of the group which is removed by an acid include—C(R₃₆)(R₃₇)(R₃₈), —C(R₃₆)(R₃₇)(OR₃₉), and —C(R₀₁)(R₀₂)(OR₃₉).

In the formulae, R₃₆ to R₃₉ each independently represent an alkyl group,a cycloalkyl group, an aryl group, an aralkyl group, or an alkenylgroup. R₃₆ and R₃₇ may be bonded to each other to form a ring.

R₀₁ to R₀₂ each independently represent a hydrogen atom, an alkyl group,a cycloalkyl group, an aryl group, an aralkyl group, or an alkenylgroup.

As the repeating unit having a group which is decomposed by the actionof an acid to produce a carboxyl group included in the resin (A), arepeating unit represented by the following Formula (AI) is preferable.

In Formula (AI),

Xa₁ represents a hydrogen atom or an alkyl group which may have asubstituent.

T represents a single bond or a divalent linking group.

Rx₁ to Rx₃ each independently represent an alkyl group (linear orbranched) or a cycloalkyl group (monocyclic or polycyclic). In a casewhere all of Rx₁ to Rx₃ represent an alkyl group (linear or branched),it is preferable that at least two of Rx₁, R_(x2), and R_(x3) representa methyl group.

Two of Rx₁ to Rx₃ may be bonded to each other to form a cycloalkyl group(monocyclic or polycyclic).

Examples of the alkyl group which may have a substituent represented byXa₁ include a methyl group or a group represented by —CH₂—R₁₁. Rnrepresents a halogen atom (for example, a fluorine atom), a hydroxylgroup, or a monovalent organic group, and examples thereof include analkyl group having 5 or less carbon atoms and an acyl group having 5 orless carbon atoms. In particular, an alkyl group having 3 or less carbonatoms is preferable, and a methyl group is more preferable. In oneaspect, Xa₁ represents preferably a hydrogen atom, a methyl group, atrifluoromethyl group, or a hydroxymethyl group.

Examples of the divalent linking group represented by T include analkylene group, a —COO-Rt- group, and a —O-Rt- group. In the formula, Rtrepresents an alkylene group or a cycloalkylene group.

T represents preferably a single bond or a —COO-Rt- group. Rt representspreferably an alkylene group having 1 to 5 carbon atoms and morepreferably a —CH₂— group, a —(CH₂)₂— group, or a —(CH₂)₃— group.

As the alkyl group represented by Rx₁ to Rx₃, an alkyl group having 1 to4 carbon atoms such as a methyl group, an ethyl group, a n-propyl group,an isopropyl group, a n-butyl group, an isobutyl group, or a t-butylgroup is preferable.

As the cycloalkyl group represented by Rx₁ to Rx₃, a monocycloalkylgroup such as a cyclopentyl group or a cyclohexyl group, or apolycycloalkyl group such as a norbornyl group, a tetracyclodecanylgroup, a tetracyclododecanyl group, or an adamantyl group is preferable.

As the cycloalkyl group which is formed by two of Rx₁ to Rx₃ beingbonded to each other, a monocycloalkyl group such as a cyclopentyl groupor a cyclohexyl group, or a polycycloalkyl group such as a norbornylgroup, a tetracyclodecanyl group, a tetracyclododecanyl group, or anadamantyl group is preferable. In particular, a monocycloalkyl grouphaving 5 or 6 carbon atoms is preferable.

In the cycloalkyl group which is formed by two of Rx₁ to Rx₃ beingbonded to each other, for example, one methylene group constituting thering may be substituted with a heteroatom such as an oxygen atom or agroup having a heteroatom such as a carbonyl group.

In the repeating unit represented by Formula (AI), for example, it ispreferable that Rx₁ represents a methyl group or an ethyl group and thatRx₂ and Rx₃ are bonded to each other to form the cycloalkyl group.

Each of the groups may have a substituent, and examples of thesubstituent include an alkyl group (having 1 to 4 carbon atoms), ahalogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbonatoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6carbon atoms), in which the number of carbon atoms is preferably 8 orless.

As the repeating unit represented by Formula (AI), an acid-decomposabletertiary alkyl (meth)acrylate repeating unit (a repeating unit in whichXa₁ represents a hydrogen atom or a methyl group, and T represents asingle bond) is preferable. A repeating unit in which Rx₁ to Rx₃ eachindependently represent a linear or branched alkyl group is morepreferable, and a repeating unit in which Rx₁ to Rx₃ each independentlyrepresent a linear alkyl group is still more preferable.

Hereinafter, specific examples of the repeating unit having a groupwhich is decomposed by the action of an acid to produce a carboxyl groupincluded in the resin (A) will be shown, but the present invention isnot limited thereto.

In the specific examples, Rx and Xa₁ represent a hydrogen atom, CH₃,CF₃, or CH₂OH. Rxa and Rxb each independently represent an alkyl grouphaving 1 to 4 carbon atoms. Z represents a substituent having a polargroup. In a case where a plurality of Z's are present, Z's eachindependently represent a substituent having a polar group. p represents0 or a positive integer. Examples of the substituent having a polargroup represented by Z include a linear or branched alkyl group having ahydroxyl group, a cyano group, an amino group, an alkylamido group, or asulfonamide group, or a cycloalkyl group. In particular, an alkyl grouphaving a hydroxyl group is preferable. As the branched alkyl group, anisopropyl group is preferable.

The content of the repeating unit having a group which is decomposed bythe action of an acid to produce a carboxyl group is preferably 15 to 90mol %, more preferably 20 to 90 mol %, still more preferably 25 to 80mol %, and even still more preferably 30 to 70 mol % with respect to allthe repeating units of the resin (A).

It is preferable that the resin (A) further includes a repeating unithaving a lactone group.

As the lactone group, any group having a lactone structure can be used.In particular, a group having a 5- to 7-membered lactone structure ispreferable. In this case, it is preferable that another ring structuremay be fused to group having a 5- to 7-membered lactone structure toform a bicyclo structure or a spiro structure.

It is preferable that the resin (A) further includes a repeating unitwhich has a group having with a lactone structure represented by any oneof the following Formulae (LC1-1) to (LC1-16). In addition, the grouphaving a lactone structure may be directly bonded to a main chain. Asthe lactone structure, a group represented by Formula (LC1-1), (LC1-4),(LC1-5), (LC1-6), (LC1-13), or (LC1-14) is preferable.

The lactone structure portion may or may not have a substituent (Rb₂).Preferable examples of the substituent (Rb₂) include an alkyl grouphaving 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbonatoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonylgroup having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, ahydroxyl group, a cyano group, and an acid-decomposable group. n₂represents an integer of 0 to 4. In a case where n₂ represents 2 ormore, a plurality of Rb₂'s may be the same as or different from eachother or may be bonded to each other to form a ring.

Examples of the repeating unit which has a group having a lactonestructure represented by any one of Formulae (LC1-1) to (LC1-16) includea repeating unit represented by the following Formula (AII).

In Formula (AII), Rb₀ represents a hydrogen atom, a halogen atom, or analkyl group having 1 to 4 carbon atoms.

Preferable examples of a substituent which may be included in the alkylgroup represented by Rb₀ include a hydroxyl group and a halogen atom.

Examples of the halogen atom represented by Rb₀ include a fluorine atom,a chlorine atom, a bromine atom, and an iodine atom. Rb₀ representspreferably a hydrogen atom or a methyl group.

Ab represents a single bond, an alkylene group, a divalent linking grouphaving a monocyclic or polycyclic alicyclic hydrocarbon structure, anether group, an ester group, a carbonyl group, a carboxyl group, or adivalent group including a combination thereof. In particular, a singlebond or a linking group represented by -Ab₁-CO₂— is preferable. Ab₁represents a linear or branched alkylene group or a monocyclic orpolycyclic cycloalkylene group and preferably a methylene group, anethylene group, a cyclohexylene group, an adamantylene group, or anorbornylene group.

V represents a group represented by any one of Formulae (LC1-1) to(LC1-16).

In the repeating unit which has a group having a lactone structure, anoptical isomer is present, and any optical isomer may be used. Inaddition, one optical isomer may be used alone, or a mixture of aplurality of optical isomers may be used. In a case where one opticalisomer is mainly used, the optical purity (ee) thereof is preferably 90or higher and more preferably 95 or higher.

Hereinafter, specific examples of the repeating unit which has a grouphaving a lactone structure will be shown, but the present invention isnot limited thereto.

(In the formulae, Rx represents H; CH₃, CH₂OH, or CF₃)

The content of the repeating unit having a lactone group is preferably 1to 65 mol %, more preferably 1 to 30 mol %, more preferably 5 to 25 mol%, and still more preferably 5 to 20 mol %, with respect to all therepeating units of the resin (A).

The resin (A) may further include a repeating unit which has an organicgroup having a polar group, in particular, a repeating unit which has analicyclic hydrocarbon structure substituted with a polar group.

As a result, substrate adhesiveness or developer affinity are improved.As the alicyclic hydrocarbon structure of the alicyclic hydrocarbonstructure substituted with a polar group, an adamantyl group, adiamantyl group, or a norbornane group is preferable. As the polargroup, a hydroxyl group or a cyano group is preferable.

Hereinafter, specific examples of the repeating unit having a polargroup will be shown, but the present invention is not limited thereto.

In a case where the resin (A) includes the repeating unit which has anorganic group having a polar group, the content thereof is preferably 1to 50 mol %, more preferably 1 to 30 mol %, still more preferably 5 to25 mol %, and even still more preferably 5 to 20 mol % with respect toall the repeating units of the resin (A).

Further, as a repeating unit other than the above-described repeatingunits, the resin (A) may include a repeating unit having a group(photoacid generating group) which generates an acid when irradiatedwith an actinic ray or radiation. In this case, it can be consideredthat the repeating unit having a photoacid generating group correspondsto a compound (B) described below that generates an acid when irradiatedwith an actinic ray or radiation.

Examples of the repeating unit include a repeating unit represented bythe following Formula (4).

R⁴¹ represents a hydrogen atom or a methyl group. L⁴¹ represents asingle bond or a divalent linking group. L⁴² represents a divalentlinking group. W represents a structural unit which is decomposed togenerate an acid at a side chain when irradiated with an actinic ray orradiation.

Hereinafter, specific examples of the repeating unit represented byFormula (4) will be shown, but the present invention is not limitedthereto.

Other examples of the repeating unit represented by Formula (4) includerepeating units described in paragraphs “0094” to “0105” ofJP2014-041327A.

In a case where the resin (A) includes the repeating unit having aphotoacid generating group, the content of the repeating unit having aphotoacid generating group is preferably 1 to 40 mol %, more preferably5 to 35 mol %, and still more preferably 5 to 30 mol % with respect toall the repeating units of the resin (A).

The resin (A) can be synthesized using an ordinary method (for example,radical polymerization). Examples of the general synthesis methodinclude: a batch polymerization method of dissolving a monomer speciesand an initiator in a solvent and heating the solution forpolymerization; and a dropping polymerization method of dropping asolution of a monomer species and an initiator dropwise to a heatedsolvent for 1 to 10 hours. Among these, a dropping polymerization methodis preferable.

Examples of the reaction solvent include: an ether such astetrahydrofuran, 1,4-dioxane, or diisopropyl ether; a ketone such asmethyl ethyl ketone or methyl isobutyl ketone; an ester solvent such asethyl acetate; an amide solvent such as dimethyl formamide ordimethylacetamide; and a solvent for dissolving an actinic ray-sensitiveor radiation-sensitive composition described below such as propyleneglycol monomethyl ether acetate, propylene glycol monomethyl ether, orcyclohexanone. It is preferable that the same solvent as that used inthe actinic ray-sensitive or radiation-sensitive composition is used forpolymerization. As a result, particle generation during storage can besuppressed.

It is preferable that the polymerization reaction is performed in aninert gas atmosphere such as nitrogen or argon. In order to initiate thepolymerization, a commercially available radical initiator (for example,an azo initiator or peroxide) is used as the polymerization initiator.As the radical initiator, an azo initiator is preferable, and examplesthereof include an azo initiator having an ester group, a cyano group,or a carboxyl group. Preferable examples of the initiator includeazobisisobutyronitrile, azobisdimethylvaleronitrile, and dimethyl2,2′-azobis(2-methylpropionate). If desired, the initiator is addedadditionally or dividedly. After completion of the reaction, thereaction product is put into a solvent, and a desired polymer iscollected using a powder or solid collecting method or the like. Thereaction concentration is 5 to 50 mass % and preferably 10 to 30 mass %.

The reaction temperature is typically 10° C. to 150° C., preferably 30°C. to 120° C., and still more preferably 60° C. to 100° C.

Examples of a method which can be used for purification include atypical method such as: a liquid-liquid extraction method in which aresidual monomer or an oligomer component is removed using a combinationof water cleaning and an appropriate solvent; a purification method in asolution state such as ultrafiltration in which substances having aspecific molecular weight or lower are extracted and removed; aredispersion method in which a residual monomer is removed by dropping aresin solution over a poor solvent to solidify the resin in the poorsolvent; and a purification method in a solid state in which a resinslurry separated by filtration is cleaned with a poor solvent.

The weight-average molecular weight of the resin (A) is preferably 1000to 200000, more preferably 3000 to 20000, and most preferably 5000 to15000 in terms of polystyrene by GPC. By adjusting the weight-averagemolecular weight to be 1000 to 200000, deterioration in heat resistanceand dry etching resistance can be prevented. In addition, deteriorationin developability and deterioration in film forming properties caused byan increase in viscosity can be prevented.

It is still more preferable that the weight-average molecular weight ofthe resin (A) is 3000 to 9500 in terms of polystyrene by GPC. Byadjusting the weight-average molecular weight to be 3000 to 9500, inparticular, a resist residue (hereinafter also referred to as “scum”) issuppressed, and a more satisfactory pattern can be formed.

The dispersity (molecular weight distribution) is typically 1 to 5,preferably 1 to 3, more preferably 1.2 to 3.0, and still more preferably1.2 to 2.0. As the dispersity decreases, the resolution and a resistshape are improved. In addition, a side wall of a resist pattern issmooth, and roughness properties are excellent.

In the actinic ray-sensitive or radiation-sensitive composition, thecontent of the resin (A) is preferably 50 to 99.9 mass % and morepreferably 60 to 99.0 mass % with respect to the total solid content ofthe actinic ray-sensitive or radiation-sensitive composition.

In addition, in the actinic ray-sensitive or radiation-sensitivecomposition, one resin (A) may be used alone, or a plurality of resins(A) may be used in combination.

In addition, the resin (A) may include a repeating unit represented bythe following Formula (VI).

In Formula (VI),

R₆₁, R₆₂, and R₆₃ each independently represent a hydrogen atom, an alkylgroup, a cycloalkyl group, a halogen atom, a cyano group, or analkoxycarbonyl group. R₆₂ may be bonded to Ar₆ to form a ring. In thiscase, R₆₂ represents a single bond or an alkylene group.

X₆ represents a single bond, —COO—, or —CONR₆₄—. R₆₄ represents ahydrogen atom or an alkyl group.

L₆ represents a single bond or an alkylene group.

Ar₆ represents a (n+1)-valent aromatic ring group, and in a case whereAr₆ is bonded to R₆₂ to form a ring, Ar₆ represents a (n+2)-valentaromatic ring group.

In a case where n represents 2 or more, Y₂'s each independentlyrepresent a hydrogen atom or a group which is removed by the action ofan acid. At least one of Y₂'s represents a group which is removed by theaction of an acid. n represents an integer of 1 to 4.

As the group which is removed by the action of an acid represented byY₂, a structure represented by Formula (VI-A) is more preferable.

Here, L₁ and L₂ each independently represent a hydrogen atom, an alkylgroup, a cycloalkyl group, an aryl group, or a group including acombination of an alkylene group and an aryl group.

M represents a single bond or a divalent linking group.

Q represents an alkyl group, a cycloalkyl group which may have aheteroatom, an aryl group which may have a heteroatom, an amino group,an ammonium group, a mercapto group, a cyano group, or an aldehydegroup.

At least two of Q, M, and L₁ may be bonded to each other to form a ring(preferably a 5- or 6-membered ring).

It is preferable that the repeating unit represented by the formula (VI)is a repeating unit represented by the following Formula (3).

In Formula (3),

Ar₃ represents an aromatic ring group.

R₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, anaryl group, an aralkyl group, an alkoxy group, an acyl group, or aheterocyclic group.

M₃ represents a single bond or a divalent linking group.

Q₃ represents an alkyl group, a cycloalkyl group, an aryl group, or aheterocyclic group. At least two of Q₃, M₃, and R₃ are bonded to eachother to form a ring.

The aromatic ring group represented by Ar₃ is the same as Ar₆ in Formula(VI) in a case where n in Formula (VI) represents 1. In this case, aphenylene group or a naphthylene group is more preferable, and aphenylene group is still more preferable.

Hereinafter, specific examples of the repeating unit represented byFormula (VI) will be shown, but the present invention is not limitedthereto.

It is also preferable that the resin (A) includes a repeating unitrepresented by the following Formula (4).

In Formula (4),

R₄₁, R₄₂, and R₄₃ each independently represent a hydrogen atom, an alkylgroup, a cycloalkyl group, a halogen atom, a cyano group, or analkoxycarbonyl group. R₄₂ may be bonded to L₄ to form a ring. In thiscase, R₄₂ represents an alkylene group.

L₄ represents a single bond or a divalent linking group. In a case whereL₄ and R₄₂ form a ring, L₄ represents a trivalent linking group.

R₄₄ and R₄₅ represent a hydrogen atom, an alkyl group, a cycloalkylgroup, an aryl group, an aralkyl group, an alkoxy group, an acyl group,or a heterocyclic group.

M₄ represents a single bond or a divalent linking group.

Q₄ represents an alkyl group, a cycloalkyl group, an aryl group, or aheterocyclic group.

At least two of Q₄, M₄, and R₄₄ are bonded to each other to form a ring.

R₄₁, R₄₂, and R₄₃ have the same definitions and the same preferableranges as R₅₁, R₅₂, and R₅₃ in Formula (V).

L₄ has the same definition and the same preferable range as L₅ inFormula (V).

R₄₄ and R₄₅ have the same definition and the same preferable range as R₃in Formula (3).

M₄ has the same definition and the same preferable range as M₃ inFormula (3).

Q₄ has the same definition and the same preferable range as Q₃ inFormula (3).

Examples of a ring which is formed by at least two of Q₄, M₄, and R₄₄being bonded to each other include the ring which is formed by at leasttwo of Q₃, M₃, and R₃ being bonded to each other, and preferable rangesthereof are also the same.

Hereinafter, specific examples of the repeating unit represented byFormula (4) will be shown, but the present invention is not limitedthereto.

In addition, the resin (A) may include a repeating unit represented bythe following Formula (BZ).

In Formula (BZ), AR represents an aryl group. Rn represents an alkylgroup, a cycloalkyl group, or an aryl group. Rn and AR may be bonded toeach other to form a nonaromatic ring.

R₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, ahalogen atom, a cyano group, or an alkyloxycarbonyl group.

Hereinafter, specific examples of the repeating unit represented by theformula (BZ) will be shown, but the present invention is not limitedthereto.

As the repeating unit having an acid-decomposable group, one kind may beused alone, or two or more kinds may be used in combination.

The content of the repeating unit having an acid-decomposable group inthe resin (A) (in a case where the resin (A) includes a plurality ofrepeating units having an acid-decomposable group, the total contentthereof) is preferably 5 mol % or higher and 80 mol % or lower, morepreferably 5 mol % or higher and 75 mol % or lower, and still morepreferably 10 mol % or higher and 65 mol % or lower with respect to allthe repeating units of the resin (A).

The resin (A) may include a repeating unit represented by the followingFormula (V) or the following Formula (VI).

In the formulae,

R₆ and R₇ each independently represent a hydrogen atom, a hydroxy group,a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms,an alkoxy group or acyloxy group, a cyano group, a nitro group, an aminogroup, a halogen atom, an ester group (—OCOR or —COOR: R represents analkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), ora carboxyl group.

n₃ represents an integer of 0 to 6.

n₄ represents an integer of 0 to 4.

X₄ represents a methylene group, an oxygen atom, or a sulfur atom.

Hereinafter, specific examples of the repeating unit represented byFormula (V) or Formula (VI) will be shown, but the present invention isnot limited thereto.

The resin (A) may further include a repeating unit having a silicon atomat a side chain. Examples of the repeating unit having a silicon atom ata side chain include a (meth)acrylate repeating unit having a siliconatom and a vinyl repeating unit having a silicon atom. The repeatingunit having a silicon atom at a side chain is typically a repeating unitwhich has a group having a silicon atom at a side chain, and examples ofthe group having a silicon atom include a trimethylsilyl group, atriethylsilyl group, a triphenylsilyl group, a tricyclohexylsilyl group,a tristrimethylsilylsiloxysilyl group, a tristrimethylsilylsilyl group,a methylbistrimethylsilylsilyl group, a methylbistrimethylsilloysilylgroup, a dimethyltrimethylsilylsilyl group, adimethyltrimethylsilloxysilyl group, a cyclic or linear polysiloxanedescribed below, and a basket-type, ladder-type, or random-typesilsesquioxane structure described below. In the formulae, R and R1 eachindependently represent a monovalent substituent. * represents a directbond.

Preferable examples of the repeating unit having the above-describedgroup include a repeating unit derived from an acrylate or methacrylatecompound having the above-described group, and a repeating unit derivedfrom a compound having the above-described group and a vinyl group.

It is preferable that the repeating unit having a silicon atom is arepeating unit having a silsesquioxane structure. As a result, excellentcollapse performance can be exhibited during the formation of anultrafine pattern (for example, line width: 50 nm or less) in which across-sectional shape has a high aspect ratio (for example, athickness/line width is 3 or more).

Examples of the silsesquioxane structure include a basket-typesilsesquioxane structure, a ladder-type silsesquioxane structure, and arandom-type silsesquioxane structure. Among these, a basket-typesilsesquioxane structure is preferable.

Here, the basket-type silsesquioxane structure refers to asilsesquioxane structure having a basket-shaped skeleton. Thebasket-type silsesquioxane structure may be a complete basket-typesilsesquioxane structure or an incomplete basket-type silsesquioxanestructure and is preferably a complete basket-type silsesquioxanestructure.

In addition, the ladder-type silsesquioxane structure refers to asilsesquioxane structure having a ladder-shaped skeleton.

In addition, the random-type silsesquioxane structure refers to asilsesquioxane structure having a random skeleton.

It is preferable that the basket-type silsesquioxane structure is asiloxane structure represented by the following Formula (S).

In Formula (S), R represents a monovalent organic group. A plurality ofR's may be the same as or different from each other.

The organic group is not particularly limited, and specific examplesthereof include a hydroxy group, a nitro group, a carboxy group, analkoxy group, an amino group, a mercapto group, a blocked mercapto group(for example, a mercapto group blocked (protected) with an acyl group),an acyl group, an imido group, a phosphino group, a phosphinyl group, asilyl group, a vinyl group, a hydrocarbon group which may have aheteroatom, a (meth)acryl group-containing group, and an epoxygroup-containing group.

Examples of the heteroatom of the hydrocarbon group which may have aheteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, and aphosphorus atom.

Examples of the hydrocarbon group of the hydrocarbon group which mayhave a heteroatom include an aliphatic hydrocarbon group, an aromatichydrocarbon group, and a group including a combination thereof.

The aliphatic hydrocarbon group may be linear, branched, or cyclic.Specific examples of the aliphatic hydrocarbon group include a linear orbranched alkyl group (particularly having 1 to 30 carbon atoms), alinear or branched alkenyl group (particularly having 2 to 30 carbonatoms), and a linear or branched alkynyl group (particularly, having 2to 30 carbon atoms).

Examples of the aromatic hydrocarbon group include an aromatichydrocarbon group having 6 to 18 carbon atoms such as a phenyl group, atolyl group, a xylyl group, or a naphthyl group.

In a case where the resin (A) includes the repeating unit which hassilicon atom at a side chain, the content thereof is preferably 1 to 30mol %, more preferably 5 to 25 mol %, and still more preferably 5 to 20mol % with respect to all the repeating units of the resin (A).

(B) Compound (Photoacid Generator) which Generates Acid by Actinic Rayor Radiation

It is preferable that the actinic ray-sensitive or radiation-sensitiveresin composition includes a compound (hereinafter, also referred to as“photoacid generator (PAG)”) which generates an acid by an actinic rayor radiation.

The photoacid generator may be a low molecular weight compound or may beincorporated into a part of a polymer. In addition, the photoacidgenerator may be a low molecular weight compound which is incorporatedinto a part of polymer.

In a case where the photoacid generator is a low molecular weightcompound, the molecular weight is preferably 3000 or lower, morepreferably 2000 or lower, and still more preferably 1000 or lower.

In a case where the photoacid generator is incorporated into a part of apolymer, the photoacid generator may be incorporated into a part of theresin (A) or another resin different from the resin (A).

In the present invention, it is preferable that the photoacid generatoris a low molecular weight compound.

The photoacid generator is not particularly limited as long as it iswell-known. As the photoacid generator, a compound, which generates anorganic acid, for example, at least one of sulfonic acid,bis(alkylsulfonyl)imide, or tris(alkylsulfonyl)methide when irradiatedwith an actinic ray or radiation and preferably an electron beam or anextreme ultraviolet ray, is preferable.

A compound represented by the following Formula (ZI), (ZII) or (ZIII) ismore preferable.

In Formula (ZI),

R₂₀₁, R₂₀₂, and R₂₀₃ each independently represent an organic group.

The number of carbon atoms in the organic group represented by R₂₀₁,R₂₀₂, and R₂₀₃ is generally 1 to 30 and preferably 1 to 20.

In addition, two of R₂₀₁ to R₂₀₃ may be bonded to each other to form aring structure, and the ring may include an oxygen atom, a sulfur atom,an ester bond, an amide bond, or a carbonyl group. Examples of the groupwhich is formed by two of R₂₀₁ to R₂₀₃ being bonded to each otherinclude an alkylene group (for example, a butylene group or a pentylenegroup).

Z⁻ represents a non-nucleophilic anion (an anion having a significantlylow ability to cause a nucleophilic reaction to occur).

Examples of the non-nucleophilic anion include a sulfonate anion (forexample, an aliphatic sulfonate anion, an aromatic sulfonate anion, or acamphor sulfonate anion), a carboxylate anion (for example, an aliphaticcarboxylate anion, an aromatic carboxylate anion, or an aralkylcarboxylate anion), a sulfonyl imide anion, a bis(alkylsulfonyl)imideanion, and a tris(alkylsulfonyl)methide anion.

An aliphatic site in the aliphatic sulfonate anion and the aliphaticcarboxylate anion may be an alkyl group or a cycloalkyl group and ispreferably a linear or branched alkyl group having 1 to 30 carbon atomsor a cycloalkyl group having 3 to 30 carbon atoms.

As the aromatic group in the aromatic sulfonate anion and the aromaticcarboxylate anion, an aryl group having 6 to 14 carbon atoms ispreferable, and examples thereof include a phenyl group, a tolyl group,and naphthyl group.

The alkyl group, the cycloalkyl group, and the aryl group describedabove may have a substituent. Specific examples of the substituentinclude a nitro group, a halogen atom such as a fluorine atom, acarboxyl group, a hydroxyl group, an amino group, a cyano group, analkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkylgroup (preferably having 3 to 15 carbon atoms), an aryl group(preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group(preferably having 2 to 7 carbon atoms), an acyl group (preferablyhaving 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferablyhaving 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15carbon atoms), an aryloxysulfonyl group (preferably having 6 to 20carbon atoms), an alkylaryloxysulfonyl group (preferably having 7 to 20carbon atoms), a cycloalkylaryloxysulfonyl group (preferably having 10to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to20 carbon atoms), and a cycloalkylalkyloxyalkyloxy group (preferablyhaving 8 to 20 carbon atoms).

Examples of an aryl group and a ring structure included in each of thegroups include an alkyl group (preferably having 1 to 15 carbon atoms)as a substituent.

As the aralkyl group in the aralkyl carboxylate anion, an aralkyl grouphaving 7 to 12 carbon atoms is preferable, and examples thereof includea benzyl group, a phenethyl group, a naphthylmethyl group, anaphthylethyl group, and a naphthylbutyl group.

Examples of the sulfonyl imide anion include a saccharin anion.

As the alkyl group in the bis(alkylsulfonyl)imide anion and thetris(alkylsulfonyl)methide anion, an alkyl group having 1 to 5 carbonatoms is preferable. Examples of a substituent of the alkyl groupinclude a halogen atom, an alkyl group substituted with a halogen atom,an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, anaryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group. Amongthese, a fluorine atom or an alkyl group substituted with a fluorineatom is preferable.

In addition, the alkyl groups in the bis(alkylsulfonyl)imide anions maybe bonded to each other to form a ring structure. As a result, the acidstrength increases.

Other examples of the non-nucleophilic anion include phosphorus fluoride(for example, PF₆ ⁻), boron fluoride (for example, BF₄ ⁻), and antimonyfluoride (for example, SbF₆ ⁻).

As the non-nucleophilic anion, an aliphatic sulfonate anion in which atleast the α-position of sulfonic acid is substituted with a fluorineatom, an aromatic sulfonate anion substituted with a fluorine atom or agroup having a fluorine atom, a bis(alkylsulfonyl)imide anion in whichthe alkyl group is substituted with a fluorine atom, or atris(alkylsulfonyl)methide anion in which the alkyl group is substitutedwith a fluorine atom is preferable. As the non-nucleophilic anion, aperfluoroaliphatic sulfonate anion (still more preferably having 4 to 8carbon atoms) or a benzenesulfonate anion having a fluorine atom is morepreferable, and a nonafluorobutanesulfonate anion, aperfluorooctanesulfonate anion, a pentafluorobenzenesulfonate anion, ora 3,5-bis(trifluoromethyl)benzenesulfonate anion is still morepreferable.

From the viewpoint of the acid strength, it is preferable that the pKaof the acid generated is −1 or lower to improve sensitivity.

In addition, as the non-nucleophilic anion, for example, an anionrepresented by the following Formula (AN1) is preferable.

In the formula,

Xf's each independently represent a fluorine atom or an alkyl groupsubstituted with at least one fluorine atom.

R¹ and R² each independently represent a hydrogen atom, a fluorine atom,or an alkyl group. In a case where a plurality of R's and a plurality ofR²'s are present, R¹'s and R²'s may be the same as or different fromeach other.

L represents a divalent linking group. In a case where a plurality ofL's are present,

L's may be the same as or different from each other.

A represents a cyclic organic group.

x represents an integer of 1 to 20, y represent an integer of 0 to 10,and z represents an integer of 0 to 10.

Formula (AN1) will be described in more detail.

As the alkyl group in the alkyl group substituted with a fluorine atomrepresented by Xf, an alkyl group having 1 to 10 carbon atoms ispreferable, and an alkyl group having 1 to 4 carbon atoms is morepreferable. In addition, as the alkyl group in the alkyl groupsubstituted with a fluorine atom represented by Xf, a perfluoroalkylgroup is preferable.

Xf represents preferably a fluorine atom or a perfluoroalkyl grouphaving or 1 to 4 carbon atoms. Specific examples of Xf include afluorine atom, CF₃, C₂F₅, C₃F₇, C₄F₉, CH₂CF₃, CH₂CH₂CF₃, CH₂C₂F₅,CH₂CH₂C₂F₅, CH₂C₃F₇, CH₂CH₂C₃F₇, CH₂C₄F₉, and CH₂CH₂C₄F₉. Among these, afluorine atom or CF₃ is preferable.

In particular, it is preferable that both Xf's represent a fluorineatom.

The alkyl group represented by R¹ and R² may have a substituent(preferably a fluorine atom), and an alkyl group having 1 to 4 carbonatoms is preferable. A perfluoroalkyl group having 1 to 4 carbon atomsis more preferable. Specific examples of the alkyl group having asubstituent represented by R¹ and R² include CF₃, C₂F₅, C₃F₇, C₄F₉,C₅F₁₁, C₆F₁₃, C₇F₁₅, C₈F₁₇, CH₂CF₃, CH₂CH₂CF₃, CH₂C₂F₅, CH₂CH₂C₂F₅,CH₂C₃F₇, CH₂CH₂C₃F₇, CH₂C₄F₉, and CH₂CH₂C₄F₉. Among these, CF₃ ispreferable.

R¹ and R² represent preferably a fluorine atom or CF₃.

x represents preferably 1 to 10 and more preferably 1 to 5.

y represents preferably 0 to 4 and more preferably 0.

z represents preferably 0 to 5 and more preferably 0 to 3.

The divalent linking group represented by L is not particularly limited,and examples thereof include —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO₂—,an alkylene group, a cycloalkylene group, an alkenylene group, a linkinggroup obtained by linking two or more kinds among the above-describedgroups linking to each other. A linking group having 12 or less carbonatoms in total is preferable. Among these, —COO—, —OCO—, —CO—, or —O— ispreferable, and —COO— or —OCO— is more preferable.

In Formula (ANI), as a combination of partial structures other than A,for example, SO³⁻—CF₂—CH₂—OCO—, SO³⁻—CF₂—CH₂—CHF—OCO—, SO³⁻—CF₂—COO—,SO³⁻—CF₂—CF₂—CH₂—, or SO³⁻—CF₂—CH(CF₃)—OCO— is preferable.

The cyclic organic group represented by A is not particularly limited aslong as it has a cyclic structure, and examples thereof include analicyclic group, an aryl group, a heterocyclic group (including not onlyan aromatic heterocyclic group but also a nonaromatic heterocyclicgroup).

The alicyclic group may be monocyclic or polycyclic, and amonocycloalkyl group such as a cyclopentyl group, a cyclohexyl group, oran cyclooctyl group, or a polycycloalkyl group such as a norbornylgroup, a tricyclodecanyl group, a tetracyclodecanyl group, atetracyclododecanyl group, or an adamantyl group is preferable. Amongthese, an alicyclic group having a bulky structure which has 7 or morecarbon atoms such as a norbornyl group, a tricyclodecanyl group, atetracyclodecanyl group, a tetracyclododecanyl group, or an adamantylgroup is preferable from the viewpoints of suppressing in-film diffusionin a heating step after exposure and improving a mask error enhancementfactor (MEEF).

Examples of the aryl group include a benzene ring, a naphthalene ring, aphenanthrene ring, and an anthracene ring.

Examples of the heterocyclic group include a furan ring, a thiophenering, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, adibenzothiophene ring, and a group derived from a pyridine ring. Amongthese, a furan ring, a thiophene ring, or a group derived from apyridine ring is preferable.

In addition, as the cyclic organic group, a lactone structure can beused, and specific examples thereof include lactone structuresrepresented by the following Formulae (LC1-1) to (LC1-17).

The cyclic organic group may have a substituent, and examples of thesubstituent include an alkyl group (a linear, branched, or cyclic alkylgroup; preferably having 1 to 12 carbon atoms), a cycloalkyl group (amonocycle, a polycycle, or a spiro ring; preferably having 3 to 20carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), ahydroxy group, an alkoxy group, an ester group, an amido group, aurethane group, an ureido group, a thioether group, a sulfonamide group,and a sulfonate group. Carbon (carbon contributing to ring formation)constituting the cyclic organic group may be carbonyl carbon.

The substituent corresponds to Rb₂ in (LC1-1) to (LC1-17). In addition,in (LC1-1) to (LC1-17), n₂ represents an integer of 0 to 4. In a casewhere n₂ represents 2 or more, a plurality of Rb₂'s may be the same asor different from each other or may be bonded to each other to form aring.

Examples of the organic group represented by R₂₀₁, R₂₀₂, and R₂₀₃ inFormula (ZI) include an aryl group, an alkyl group, and a cycloalkylgroup.

It is preferable that at least one of R₂₀₁, R₂₀₂, or R₂₀₃ represents anaryl group, and it is more preferable that all of R₂₀₁, R₂₀₂, or R₂₀₃represent an aryl group. As the aryl group, not only a phenyl group or anaphthyl group but also a heteroaryl group such as an indole residue ora pyrrole residue may be used. As the alkyl group and the cycloalkylgroup represented by R₂₀₁ to R₂₀₃, a linear or branched alkyl grouphaving 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbonatoms is preferable. As the alkyl group, a methyl group, an ethyl group,a n-propyl group, an i-propyl group, or a n-butyl group is morepreferable. As the cycloalkyl group, a cyclopropyl group, a cyclobutylgroup, a cyclopentyl group, a cyclohexyl group, or a cycloheptyl groupis more preferable. Each of the groups may further have a substituent.Examples of the substituent include a nitro group, a halogen atom suchas a fluorine atom, a carboxyl group, a hydroxyl group, an amino group,a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms),a cycloalkyl group (preferably having 3 to 15 carbon atoms), an arylgroup (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group(preferably having 2 to 7 carbon atoms), an acyl group (preferablyhaving 2 to 12 carbon atoms), and an alkoxycarbonyloxy group (preferablyhaving 2 to 7 carbon atoms), but the present invention is not limitedthereto.

Next, Formulae (ZII) and (ZIII) will be described.

In Formulae (ZII) and (ZIII), R₂₀₄ to R₂₀₇ each independently representan aryl group, an alkyl group, or a cycloalkyl group.

As the aryl group represented by R₂₀₄ to R₂₀₇, a phenyl group or anaphthyl group is preferable, and a phenyl group is more preferable. Thearyl group represented by R₂₀₄ to R₂₀₇, may be an aryl group which has aheterocyclic structure having an oxygen atom, a nitrogen atom, or asulfur atom. Examples of a skeleton of the aryl group having aheterocyclic structure include pyrrole, furan, thiophene, indole,benzofuran, and benzothiophene.

Preferable examples of the alkyl group and the cycloalkyl grouprepresented by R₂₀₄ to R₂₀₇ include a linear or branched alkyl grouphaving 1 to 10 carbon atoms (for example, a methyl group, an ethylgroup, a propyl group, a butyl group or a pentyl group), and acycloalkyl group having 3 to 10 carbon atoms (a cyclopentyl group, acyclohexyl group, or a norbornyl group).

The aryl group, the alkyl group, and the cycloalkyl group represented byR₂₀₄ to R₂₀₇ may have a substituent. Examples of the substituent whichmay be included in the aryl group, the alkyl group, and the cycloalkylgroup represented by R₂₀₄ to R₂₀₇ include an alkyl group (for example,having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3to 15 carbon atoms), an aryl group (for example, having 6 to 15 carbonatoms), an alkoxy group (for example, having 1 to 15 carbon atoms), ahalogen atom, a hydroxyl group, and a phenylthio group.

In addition, Z⁻ in Formula (ZII) represents a non-nucleophilic anion.Specifically, Z⁻ in Formula (ZII) has the same definition and the samepreferable aspect as Z⁻ in Formula (ZI).

Hereinafter, specific examples of Formulae (ZI) to (ZIII) will be shownbelow, but the present invention is not limited thereto.

In the present invention, from the viewpoint of suppressing diffusion ofan acid generated by exposure to a non-exposed portion and improvingresolution, the photoacid generator is preferably a compound whichgenerates an acid (more preferably sulfonic acid) having a volume of 130Å³ or higher when irradiated with an electron beam or an extremeultraviolet ray, more preferably a compound which generates an acid(more preferably sulfonic acid) having a volume of 190 Å³ or higher,still more preferably a compound which generates an acid (morepreferably sulfonic acid) having a volume of 270 Å³ or higher, and evenstill more preferably a compound which generates an acid (morepreferably sulfonic acid) having a volume of 400 Å³ or higher. From theviewpoints of sensitivity and coating solvent solubility, the volume ispreferably 2000 Å³ or lower and more preferably 1500 Å³ or lower. Avalue of the volume is obtained using “WinMOPAC” (manufactured byFUJITSU). That is, a chemical structure of an acid according to eachexample is input. Next, the most stable conformation of each acid isdetermined through a molecular field calculation using a MM3 method withthe input chemical structure as an initial structure. Next, a molecularorbital calculation is performed on the most stable conformation using aPM3 method. As a result, “accessible volume” of each acid can becalculated.

In the present invention, the following examples of the photoacidgenerators which generate an acid when irradiated with an actinic ray orradiation are preferable. In some of the examples, a calculated value ofthe volume is added (unit: Å³). The calculated value herein denotes avalue of an acid in which a proton is bonded to the anion portion.

The details of the photoacid generator can be found in paragraphs “0368”to “0377” of JP2014-41328A and paragraphs “0240” to “0262” ofJP2013-228681A (corresponding to paragraph “0339” of US2015/004533A),the content of which is incorporated herein by reference. In addition,specific preferable examples include the following compounds, but thepresent invention is not limited thereto.

As the photoacid generator, one kind may be used alone, or two or morekinds may be used in combination.

The content of the photoacid generator in the actinic ray-sensitive orradiation-sensitive resin composition is preferably 0.1 to 50 mass %,more preferably 5 to 50 mass %, and still more preferably 8 to 40 mass %with respect to the total solid content of the composition. Inparticular, in order to simultaneously realize high sensitivity and highresolution during irradiation of an electron beam or an extremeultraviolet ray, the content of the photoacid generator is preferablyhigh, more preferably 10 to 40 mass %, and still more preferably 10 to35 mass %.

(C) Solvent

In order to dissolve the respective components to prepare the actinicray-sensitive or radiation-sensitive resin composition, a solvent can beused. Examples of the solvent used include an organic solvent such asalkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkylether, alkyl lactate, alkyl alkoxy propionate, cyclic lactone having 4to 10 carbon atoms, a monoketone compound having 4 to 10 carbon atomswhich may include a ring, alkylene carbonate, alkyl alkoxy acetate, oralkyl pyruvate.

Preferable examples of the alkylene glycol monoalkyl ether carboxylateinclude propylene glycol monomethyl ether acetate, propylene glycolmonoethyl ether acetate, propylene glycol monopropyl ether acetate,propylene glycol monobutyl ether acetate, propylene glycol monomethylether propionate, propylene glycol monoethyl ether propionate, ethyleneglycol monomethyl ether acetate, and ethylene glycol monoethyl etheracetate.

Preferable examples of the alkylene glycol monoalkyl ether includepropylene glycol monomethyl ether, propylene glycol monoethyl ether,propylene glycol monopropyl ether, propylene glycol monobutyl ether,ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

Preferable examples of the alkyl lactate include methyl lactate, ethyllactate, propyl lactate, and butyl lactate.

Preferable examples of the alkyl alkoxy propionate include ethyl3-ethoxypropionate, methyl 3-methoxypropionate, methyl3-ethoxypropionate, and ethyl 3-methoxypropionate.

Preferable examples of the cyclic lactone having 4 to 10 carbon atomsinclude β-propiolactone, β-butyrolactone, γ-butyrolactone,α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone,γ-caprolactone, γ-octanoic lactone, and α-hydroxy-γ-butyrolactone.

Preferable examples of the monoketone compound having 4 to 10 carbonatoms which may include a ring include 2-butanone, 3-methylbutanone,pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone,4-methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone,2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone,3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone,2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone,2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone,3-decanone, 4-decanone, 5-hexen-2-one, 3-penten-2-one, cyclopentanone,2-methylcyclopentanone, 3-methylcyclopentanone,2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone,cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone,4-ethylcyclohexanone, 2,2-dimethylcyclohexanone,2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone,2-methylcycloheptanone, and 3-methylcycloheptanone.

Preferable examples of the alkylene carbonate include propylenecarbonate, vinylene carbonate, ethylene carbonate, and butylenecarbonate.

Preferable examples of the alkyl alkoxy acetate include 2-methoxyethylacetate, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate,3-methoxy-3-methylbutyl acetate, and 1-methoxy-2-propyl acetate.

Preferable examples of the alkyl pyruvate include methyl pyruvate, ethylpyruvate, and propyl pyruvate.

Preferable examples of the solvent which can be used include a solventhaving a boiling point of 130° C. or higher at a normal temperatureunder a normal pressure. Specific examples of the solvent includecyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethyleneglycol monoethyl ether acetate, propylene glycol monomethyl etheracetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethylacetate, 2-(2-ethoxyethoxy)ethyl acetate, and propylene carbonate.

In the present invention, as the solvent, one kind may be used alone, ortwo or more kinds may be used in combination.

In the present invention, as the organic solvent, a mixed solvent inwhich a solvent having a hydroxyl group in a structure is mixed with asolvent having no hydroxyl group may be used.

Examples of the solvent having a hydroxyl group include ethylene glycol,ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,propylene glycol, propylene glycol monomethyl ether, propylene glycolmonoethyl ether, and ethyl lactate. Among these, propylene glycolmonomethyl ether or ethyl lactate is preferable.

Examples of the solvent having no hydroxyl group include propyleneglycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone,γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone,N,N-dimethylacetamide, and dimethyl sulfoxide. Among these, propyleneglycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone,γ-butyrolactone, cyclohexanone, or butyl acetate is more preferable, andpropylene glycol monomethyl ether acetate, ethyl ethoxypropionate,2-heptanone is most preferable.

A mixing ratio (mass) of the solvent having a hydroxyl group to thesolvent having no hydroxyl group is preferably 1/99 to 99/1, morepreferably 10/90 to 90/10, and still more preferably 20/80 to 60/40 bymass. In particular, a mixed solvent including 50 mass % or higher ofthe solvent having no hydroxyl group is preferable from the viewpoint ofcoating uniformity.

It is preferable that the solvent is a mixed solvent including two ormore propylene glycol monomethyl ether acetates.

As the solvent, for example, a solvent described in paragraphs “0013” to“0029” of JP2014-219664A can also be used.

(D) Basic Compound

In order to reduce a change in performance with the lapse of time fromexposure to heating, it is preferable that the actinic ray-sensitive orradiation-sensitive resin composition includes a basic compound (D).

Preferable examples of the basic compound (D) include compounds havingstructures represented by the following Formulae (A) to (E).

In Formulae (A) and (E), R²⁰⁰, R²⁰¹, and R²⁰² may be the same as ordifferent from each other and each independently represent a hydrogenatom, an alkyl group (preferably having 1 to 20 carbon atoms), acycloalkyl group (preferably having 3 to 20 carbon atoms), or an arylgroup (preferably having 6 to 20 carbon atoms). Here, R²⁰¹ and R²⁰² maybe bonded to each other to form a ring.

As the alkyl group having a substituent, an aminoalkyl group having 1 to20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or acyanoalkyl group having 1 to 20 carbon atoms is preferable.

R²⁰³, R²⁰⁴, R²⁰⁵, and R²⁰⁶ may be the same as or different from eachother and each independently represent an alkyl group having 1 to 20carbon atoms.

It is more preferable that the alkyl group in the Formulae (A) and (E)is unsubstituted.

Examples of a preferable compound include guanidine, aminopyrrolidine,pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine,and piperidine. Examples of a more preferable compound include acompound having an imidazole structure, a diazabicyclo structure, anonium hydroxide structure, an onium carboxylate structure, atrialkylamine structure, an aniline structure, or a pyridine structure,an alkylamino derivative having a hydroxyl group and/or an ether bond,and an aniline derivative having a hydroxyl group and/or an ether bond.

Examples of the compound having an imidazole structure includeimidazole, 2,4,5-triphenylimidazole, and benzimidazole. Examples of thecompound having a diazabicyclo structure include1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]nona-5-ene, and1,8-diazabicyclo[5,4,0]undeca-7-ene. As the compound having an oniumhydroxide structure, for example, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, or sulfonium hydroxide having a 2-oxoalkyl groupcan be used, and specific examples thereof include triphenylsulfoniumhydroxide, tris(t-butylphenyl)sulfonium hydroxide,bis(t-butylphenyl)iodonium hydroxide, phenacyl thiophenium hydroxide,and 2-oxopropylthiophenium hydroxide. As the compound having an oniumcarboxylate structure, for example, a compound obtained by carboxylationof the anion site of a compound having an omnium hydroxide structure canbe used, and examples thereof include acetate, adamantane-1-carboxylate,and perfluoroalkyl carboxylate. Examples of the compound havingtrialkylamine structure include tri-(n-butyl)amine andtri-(n-octyl)amine. Examples of the compound having an aniline structureinclude 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline,and N,N-dihexylaniline. Examples of the alkylamino derivative having ahydroxyl group and/or an ether bond include ethanolamine,diethanolamine, triethanolamine, and tris(methoxyethoxyethyl)amine.Examples of the aniline derivative having a hydroxyl group and/or anether bond include N,N-bis(hydroxyethyl)aniline.

Other preferable examples of the basic compound include an aminecompound having a phenoxy group and an ammonium salt compound having aphenoxy group.

As the amine compound, a primary, secondary, or tertiary amine compoundcan be used, and an amine compound in which at least one alkyl group isbonded to a nitrogen atom is preferable. It is more preferable that theamine compound is a tertiary amine compound. In the amine compound, aslong as at least one alkyl group (preferably having 1 to 20 carbonatoms) is bonded to a nitrogen atom, in addition to the alkyl group, acycloalkyl group (preferably having 3 to 20 carbon atoms) or an arylgroup (preferably 6 to 12 carbon atoms) may be bonded to a nitrogenatom.

In addition, it is preferable that the amine compound has an oxygen atomat an alkyl chain to form an oxyalkylene group. The number ofoxyalkylene groups is 1 or more, preferably 3 to 9, and still morepreferably 4 to 6 in a molecule. Among the oxyalkylene groups, anoxyethylene group (—CH₂CH₂O—) or an oxypropylene group (—CH(CH₃)CH₂O— or—CH₂CH₂CH₂O—) is preferable, and an oxyethylene group is morepreferable.

As the ammonium salt compound, a primary, secondary, tertiary, orquaternary ammonium salt compound can be used, and an ammonium saltcompound in which at least one alkyl group is bonded to a nitrogen atomis preferable. In the ammonium salt compound, as long as at least onealkyl group (preferably having 1 to 20 carbon atoms) is bonded to anitrogen atom, in addition to the alkyl group, a cycloalkyl group(preferably having 3 to 20 carbon atoms) or an aryl group (preferably 6to 12 carbon atoms) may be bonded to a nitrogen atom.

In addition, it is preferable that the ammonium salt compound has anoxygen atom at an alkyl chain to form an oxyalkylene group. The numberof oxyalkylene groups is 1 or more, preferably 3 to 9, and still morepreferably 4 to 6 in a molecule. Among the oxyalkylene groups, anoxyethylene group (—CH₂CH₂O—) or an oxypropylene group (—CH(CH₃)CH₂O— or—CH₂CH₂CH₂O—) is preferable, and an oxyethylene group is morepreferable.

Examples of an anion of the ammonium salt compound include a halogenatom, a sulfonate, a borate, and a phosphate. Among these, a halogenatom or a sulfonate is preferable. As the halogen atom, a chloride, abromide, or an iodide is preferable. As the sulfonate, an organicsulfonate having 1 to 20 carbon atoms is preferable. Examples of theorganic sulfonate include an alkyl sulfonate having 1 to 20 carbon atomsand an aryl sulfonate. The alkyl group of the alkyl sulfonate may have asubstituent, and examples of the substituent include fluorine, chlorine,bromine, an alkoxy group, an acyl group, and an aryl group. Specificexamples of the alkyl sulfonate include methane sulfonate, ethanesulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzylsulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, andnonafluorobutane sulfonate. Examples of the aryl group of the arylsulfonate include a benzene ring, a naphthalene ring, and an anthracenering. The benzene ring, the naphthalene ring, and the anthracene ringmay have a substituent. As the substituent, a linear or branched alkylgroup having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6carbon atoms is preferable. Specific examples of the linear or branchedalkyl group and the cycloalkyl group include methyl, ethyl, n-propyl,isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, and cyclohexyl. Otherexamples of the substituent include an alkoxy group having 1 to 6 carbonatoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxygroup.

The amine compound having a phenoxy group or the ammonium salt compoundhaving a phenoxy group denotes an amine compound or an ammonium saltcompound having a phenoxy group at a terminal of an alkyl group oppositeto a nitrogen atom. The phenoxy group may have a substituent. Examplesof the substituent of the phenoxy group include an alkyl group, analkoxy group, a halogen atom, a cyano group, a nitro group, a carboxylgroup, a carboxylate group, a sulfonate group, an aryl group, an aralkylgroup, an acyloxy group, and an aryloxy group. The substitution positionof the substituent may be any one of the 2- to 6-position. The number ofsubstituents is 1 to 5.

It is preferable that at least one oxyalkylene group is present betweena phenoxy group and a nitrogen atom. The number of oxyalkylene groups is1 or more, preferably 3 to 9, and still more preferably 4 to 6 in amolecule. Among the oxyalkylene groups, an oxyethylene group (—CH₂CH₂O—)or an oxypropylene group (—CH(CH₃)CH₂O— or —CH₂CH₂CH₂O—) is preferable,and an oxyethylene group is more preferable.

The amine compound having a phenoxy group can be obtained by heating aprimary or secondary amine having a phenoxy group and haloalkyl ether toreact with each other, adding an aqueous solution of a strong base suchas sodium hydroxide, potassium hydroxide, or tetraalkylammonium to theobtained reaction product, and performing extraction with an organicsolvent such as ethyl acetate or chloroform. Alternatively, the aminecompound having a phenoxy group can be obtained by heating a primary orsecondary amine and haloalkyl ether having a phenoxy group at a terminalto react with each other, adding an aqueous solution of a strong basesuch as sodium hydroxide, potassium hydroxide, or tetraalkylammonium tothe obtained reaction product, and performing extraction with an organicsolvent such as ethyl acetate or chloroform.

(Compound (PA) having Proton-accepting Functional Group which isdecomposed to generate Compound in which Proton Accepting Propertiesdeteriorate, disappear, or change to Acidic Properties when irradiatedwith Actinic Ray or Radiation)

The composition according to the present invention may further include,as a basic compound, a compound [hereinafter, also referred to as“compound (PA)” ] having a proton-accepting functional group which isdecomposed to generate a compound in which proton accepting propertiesdeteriorate, disappear, or change to acidic properties when irradiatedwith an actinic ray or radiation.

The proton-accepting functional group denotes a functional group havinga group or an electron which can electrostatically interact with aproton, for example, a functional group which has a macrocyclicstructure such as cyclic polyether or a functional group which has anitrogen atom having an unshared electron pair not contributing toR-conjugation. Examples of the nitrogen atom having an unshared electronpair not contributing to R-conjugation include a nitrogen atom having apartial structure represented by the following formula.

Preferable examples of a partial structure of the proton-acceptingfunctional group include crown ether, azacrown ether, primary totertiary amine, pyridine, imidazole, and a pyrazine structure.

The compound (PA) is decomposed to generate a compound in which protonaccepting properties deteriorate, disappear, or change to acidicproperties when irradiated with an actinic ray or radiation. Here,proton accepting properties deteriorating, disappearing, or changing toacidic properties represents a change in proton accepting propertiescaused by adding a proton to the proton-accepting functional group, andspecifically represents that, when a proton adduct is generated usingthe compound (PA) having a proton-accepting functional group and aproton, an equilibrium constant in the equilibrium constant is reduced.

Specific examples of the compound (PA) include the following compounds.Further, specific examples of the compound (PA) include compoundsdescribed in paragraphs “0421” to “0428” of JP2014-41328A and paragraphs“0108” to “0116” of JP2014-134686A, the content of which is incorporatedherein by reference.

Among the basic compounds, one kind may be used alone, or two or morekinds may be used in combination.

The amount of the basic compound used is typically 0.001 to 10 mass %and preferably 0.01 to 5 mass % with respect to the solid content of theactinic ray-sensitive or radiation-sensitive composition.

It is preferable that a ratio (molar ratio; photoacid generator/basiccompound) of the photoacid generator used to the basic compound used inthe composition is 2.5 to 300. That is, the molar ratio is preferably2.5 or higher from the viewpoints of sensitivity and resolution, and ispreferably 300 or lower from the viewpoint of suppressing deteriorationin resolution caused by thickening of a resist pattern with the lapse oftime until a heating treatment after exposure. The molar ratio(photoacid generator/basic compound) is more preferably 5.0 to 200 andstill more preferably 7.0 to 150.

As the basic compound, for example, a compound (for example, an aminecompound, an amido group-containing compound, a urea compound, or anitrogen-containing heterocyclic compound) described in paragraphs“0140” to “0144” of JP2013-11833A can be used.

(A′) Hydrophobic Resin

The actinic ray-sensitive or radiation-sensitive resin composition mayinclude a hydrophobic resin (A′) in addition to the resin (A).

It is preferable that the hydrophobic resin is designed to be localizedon a surface of a resist film. Unlike the surfactant, the hydrophobicresin does not necessarily have a hydrophilic group in a molecule anddoes not necessarily contribute to uniform mixing with a polar/non-polarmaterial.

Examples of an effect obtained by the addition of the hydrophobic resininclude an effect of suppressing a static/dynamic contact angle of aresist film surface with respect to water and an effect of suppressingout gas.

From the viewpoint of localization on the film surface layer, thehydrophobic resin includes preferably one or more kinds and morepreferably two or more kinds among “a fluorine atom”, “a silicon atom”,and “a CH₃ partial structure included in a side chain of the resin”. Inaddition, it is preferable that the hydrophobic resin includes ahydrocarbon group having 5 or more carbon atoms. These groups may bepresent at a main chain of the resin or may be substituted with a sidechain.

In a case where the hydrophobic resin includes a fluorine atom and/or asilicon atom, the fluorine atom and/or the silicon atom in thehydrophobic resin may be present at a main chain or a side chain of theresin.

In a case where the hydrophobic resin includes a fluorine atom, it ispreferable that a partial structure having a fluorine atom is a resinthat has an alkyl group having a fluorine atom, a cycloalkyl grouphaving a fluorine atom, or an aryl group having a fluorine atom.

The alkyl group having a fluorine atom (preferably having 1 to 10 carbonatoms and more preferably having 1 to 4 carbon atoms) is a linear orbranched alkyl group in which at least one hydrogen atom is substitutedwith a fluorine atom and may further have a substituent other than afluorine atom.

The cycloalkyl group having a fluorine atom is a monocyclic orpolycyclic cycloalkyl group in which at least one hydrogen atom issubstituted with a fluorine atom and may further have a substituentother than a fluorine atom.

Examples of the aryl group having a fluorine atom include an aryl group,such as a phenyl group or a naphthyl group, in which at least onehydrogen atom is substituted with a fluorine atom. The aryl group havinga fluorine atom may further have a substituent other than a fluorineatom.

Examples of a repeating unit having a fluorine atom or a silicon atominclude a repeating unit described in paragraph “0519” ofUS2012/0251948A1.

In addition, as described above, it is preferable that the hydrophobicresin includes a CH₃ partial structure at a side chain.

Here, examples of the CH₃ partial structure included at a side chain ofthe hydrophobic resin include a CH₃ partial structure such as an ethylgroup or a propyl group.

On the other hand, a methyl group (for example, an α-methyl group of arepeating unit having a methacrylic acid structure) which is directlybonded to a main chain of the hydrophobic resin has little contributionto the surface localization of the hydrophobic resin caused by theeffect of the main chain, and thus is not included in examples of theCH₃ partial structure according to the present invention.

The details of the hydrophobic resin can be found in paragraphs “0348”to “0415” of JP2014-010245A, the content of which is incorporated hereinby reference.

As the hydrophobic resin, resins described in JP2011-248019A,JP2010-175859A, and JP2012-032544A can also be preferably used.

(E) Surfactant

The actinic ray-sensitive or radiation-sensitive resin composition mayfurther include a surfactant (E). By the actinic ray-sensitive orradiation-sensitive composition including the surfactant, particularlyin a case where an exposure light source having a wavelength of 250 nmor shorter, in particular, 220 nm or shorter is used, a pattern havingadhesiveness and reduced development defects can be formed with highsensitivity and resolution.

As the surfactant, a fluorine surfactant and/or a silicon surfactant ispreferably used.

Examples of the fluorine surfactant and/or the silicon surfactantinclude surfactants described in paragraph “0276” of US2008/0248425A. Inaddition, F-TOP EF301 or EF303 (manufactured by Shin-akita Chemical Co.,Ltd.); FLUORAD FC430, 431 or 4430 (manufactured by Sumitomo 3M Ltd.);MEGAFACE F171, F173, F176, F189, F113, F110, F177, F120, or R08(manufactured by DIC Corporation); SURFLON 5-382, SC101, 102, 103, 104,105, or 106 (manufactured by Asahi Glass Co., Ltd.); TROYSOL S-366(manufactured by Troy Corporation); GF-300 or GF-150 (manufactured byToagosei Co., Ltd.); SURFLON 5-393 (manufactured by AGC Seimi ChemicalCo., Ltd.); F-TOP EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351,EF352, EF801, EF802, or EF601 (manufactured by Gemco Inc.); PF636,PF656, PF6320, or PF6520 (manufactured by OMNOVA Corp.); or FTX-204G,208G, 218G, 230G, 204D, 208D, 212D, 218D, or 222D (manufactured by NeosCo., Ltd.) may be used. A polysiloxane polymer KP-341 (manufactured byShin-Etsu Chemical Co., Ltd.) can also be used as the siliconsurfactant.

In addition, in addition to the above-described surfactants, asurfactant may be synthesized using a fluoro aliphatic compoundmanufactured using a telomerization method (also referred to as atelomer method) or an oligomerization method (also referred to as anoligomer method). Specifically, a polymer including a fluoro aliphaticgroup derived from fluoro aliphatic compound may be used as thesurfactant. This fluoro aliphatic compound can be synthesized, forexample, using a method described in JP2002-90991A.

In addition, a surfactant other than a fluorine surfactant and/or asilicon surfactant which is described in paragraph “0280” ofUS2008/0248425A may be used.

Among these surfactants, one kind may be used alone, or two or morekinds may be used in combination.

In a case where the actinic ray-sensitive or radiation-sensitive resincomposition includes the surfactant, the content of the surfactant ispreferably 0 to 2 mass %, more preferably 0.0001 to 2 mass %, and stillmore preferably 0.0005 to 1 mass % with respect to the total solidcontent of the composition.

(F) Other Additives

The actinic ray-sensitive or radiation-sensitive resin composition mayfurther include a dissolution inhibiting compound, a dye, a plasticizer,a photosensitizer, a light absorber, and/or a compound for promotingsolubility in the developer (for example, a phenol compound having amolecular weight of 1000 or lower, or an aliphatic or alicyclic compoundhaving a carboxy group).

The actinic ray-sensitive or radiation-sensitive resin composition mayfurther include a dissolution inhibiting compound.

Here, “dissolution inhibiting compound” denotes a compound having amolecular weight of 3000 or lower which is decomposed by the action ofan acid such that the solubility in the organic developer decreases.

[Upper Layer Film (Top Coat Film)]

In the pattern forming method according to the present invention, anupper layer film (top coat film) may be formed over the resist film.

It is preferable that the upper layer film is not mixed with the resistfilm and is uniformly formed above the resist film.

The upper layer film is not particularly limited, and well-known upperlayer film of the related art can be formed using a well-known method ofthe related art. For example, the upper layer film can be formed basedon the description of paragraphs “0072” to “0082” of JP2014-059543A. Asa material forming the upper layer film, for example, a polymerdescribed in paragraph “0072” of JP2014-059543A or a hydrophobic resincan be used. As the hydrophobic resin, for example, the above-describedhydrophobic resin (A′) can be used.

In a case where the developer including the organic solvent is used inthe development step, it is preferable that, for example, an upper layerfilm including a basic compound described in JP2013-61648A is formed onthe resist film. Specific examples of the basic compound which may beincluded in the upper layer film include a basic compound (E) describedbelow.

In addition, it is preferable that the upper layer film includes acompound which includes at least one group or one bond selected from thegroup consisting of an ether bond, a thioether bond, a hydroxyl group, athiol group, a carbonyl bond, and an ester bond.

Further, the upper layer film may include a photoacid generator. As thephotoacid generator, the same photoacid generator (for example, theabove-described photoacid generator (B)) which may be included in theactinic ray-sensitive or radiation-sensitive composition can be used.

Hereinafter, a preferable resin which can be used in the upper layerfilm (top coat film) will be described.

(Resin)

It is preferable that the upper layer film-forming composition includesa resin. The resin which may be included in the upper layer film-formingcomposition is not particularly limited, and the same resin as thehydrophobic resin which may be included in the actinic ray-sensitive orradiation-sensitive composition (for example, the above-describedhydrophobic resin (A′)) can be used.

The details of the hydrophobic resin can be found in paragraphs “0017”to “0023” of JP2013-61647A (corresponding to paragraphs “0017” to “0023”of US2013/244438A) and in paragraphs “0016” to “0165” of JP2014-56194A,the content of which is incorporated herein by reference.

In the present invention, it is preferable that the upper layerfilm-forming composition includes a resin that includes a repeating unithaving an aromatic ring. By the upper layer film-forming compositionincluding the repeating unit having an aromatic ring, in particular,during exposure of an electron beam or an EUV ray, the generationefficiency of secondary electrons and the generation of efficiency of anacid from the compound which generates an acid by actinic ray orradiation are improved, and an effect of improving sensitivity andresolution during the formation of a pattern can be expected.

The weight-average molecular weight of the resin is preferably 3000 to100000, more preferably 3000 to 30000, and most preferably 5000 to20000. The mixing amount of the resin in the upper layer film-formingcomposition is preferably 50 to 99.9 mass %, more preferably 60 to 99.0mass %, still more preferably 70 to 99.7 mass %, and even still morepreferably 80 to 99.5 mass % with respect to the total solid content.

In a case where the upper layer film-forming composition (top coatcomposition) includes a plurality of resins, it is preferable that upperlayer film-forming composition includes at least one resin (XA) having afluorine atom and/or a silicon atom.

Regarding a preferable range of the content of the fluorine atom and thesilicon atom included in the resin (XA), the content of a repeating unithaving a fluorine atom and/or a silicon atom in the resin (XA) ispreferably 10 to 100 mass %, preferably 10 to 99 mol %, and morepreferably 20 to 80 mol %.

In addition, it is more preferable that the upper layer film-formingcomposition includes at least one resin (XA) having a fluorine atomand/or a silicon atom and a resin (XB) in which the content of afluorine atom and/or a silicon atom is lower than that of the resin(XA). As a result, during the formation of the upper layer film, theresin (XA) is eccentrically present on the surface of the upper layerfilm. Therefore, the performance such as developing characteristics orfollowability of immersion liquid can be improved.

The content of the resin (XA) is preferably 0.01 to 30 mass %, morepreferably 0.1 to 10 mass %, still more preferably 0.1 to 8 mass %, andeven still more preferably 0.1 to 5 mass % with respect to the totalsolid content of the upper layer film-forming composition. The contentof the resin (XB) is preferably 50.0 to 99.9 mass %, more preferably 60to 99.9 mass %, still more preferably 70 to 99.9 mass %, and even stillmore preferably 80 to 99.9 mass % with respect to the total solidcontent of the upper layer film-forming composition.

It is preferable that the resin (XB) does not substantially include afluorine atom and a silicon atom. In this case, specifically, the totalcontent of a repeating unit having a fluorine atom and a repeating unithaving a silicon atom is preferably 0 to 20 mol %, more preferably 0 to10 mol %, still more preferably 0 to 5 mol %, even still more preferably0 to 3 mol %, and ideally 0 mol % (that is, a fluorine atom and asilicon atom are not included) with respect to all the repeating unitsof the resin (XB).

<Method of Preparing Upper Layer Film-Forming Composition (Top CoatComposition)>

It is preferable that the respective components of the upper layerfilm-forming composition are dissolved in a solvent and are filteredthrough a filter. As the filter, a filter formed ofpolytetrafluoroethylene, polyethylene, or nylon and having a pore sizeof preferably 0.1 μm or less, more preferably 0.05 μm or less, and stillmore preferably 0.03 μm or less is preferable. A plurality of filtersmay be connected in series or in parallel. In addition, the compositionmay be filtered multiple times, and a step of filtering variousmaterials multiple times may be a cycle filtration step. Further, beforeand after the filter filtration, degassing or the like may be performedon the composition. It is preferable that the upper layer film-formingcomposition does not include impurities such as metal. The content ofthe metal components in the materials is preferably 10 ppm or lower,more preferably 5 ppm or lower, and still more preferably 1 ppm orlower, and it is still most preferable that the materials do notsubstantially include the metal components (the measured value is lowerthan a detection limit value of a measuring device).

In a case where immersion exposure is performed in the <exposure step>,the upper layer film is disposed between the actinic ray-sensitive orradiation-sensitive film and functions as a layer that prevents directcontact between the actinic ray-sensitive or radiation-sensitive filmand the immersion liquid. In this case, preferable characteristics ofthe upper layer film (upper layer film-forming composition) includesuitability for application to the actinic ray-sensitive orradiation-sensitive film, transparency to radiation, particularly, lightat 193 nm, and insolubility in the immersion liquid (preferably water).In addition, it is preferable that the upper layer film is uniformlyapplied to the surface of the actinic ray-sensitive orradiation-sensitive film without being mixed with the actinicray-sensitive or radiation-sensitive film.

In order to uniformly apply the upper layer film-forming composition tothe surface of the actinic ray-sensitive or radiation-sensitive filmwithout dissolving the actinic ray-sensitive or radiation-sensitivefilm, it is preferable that the upper layer film-forming compositionincludes a solvent in which the actinic ray-sensitive orradiation-sensitive film is not soluble. As the solvent in which theactinic ray-sensitive or radiation-sensitive film is not soluble, it ismore preferable that a solvent having different components from those ofa developer (organic developer) including an organic solvent is used.

An application method of the upper layer film-forming composition is notparticularly limited, and a spin coating method, a spray coating method,a roller coating method, or a dipping method that is well-known in therelated art can be used.

The thickness of the upper layer film is not particularly limited, andfrom the viewpoint of transparency to an exposure light source, istypically 5 nm to 300 nm, preferably 10 nm to 300 nm, more preferably 20nm to 200 nm, and still more preferably 30 nm to 100 nm.

After the formation of the upper layer film, the substrate is optionallyheated (PB).

From the viewpoint of resolution, it is preferable that the refractiveindex of the upper layer film is close to the refractive index of theactinic ray-sensitive or radiation-sensitive film.

It is preferable that the upper layer film is insoluble in the immersionliquid, and it is more preferable that the upper layer film is insolublein water.

From the viewpoint of followability of immersion liquid, the recedingcontact angle (23° C.) of the immersion liquid on the upper layer filmis preferably 50 to 100 degrees and more preferably 80 to 100 degrees.

During the immersion exposure, it is necessary that the immersion liquidmoves on a wafer following a movement of an exposure head that scans thewafer with high speed to form an exposure pattern. Therefore, thecontact angle of the immersion liquid on the actinic ray-sensitive orradiation-sensitive film in a dynamic state is important, and it ispreferable that the receding contact angle is in the above-describedrange in order to obtain higher resist performance.

In a case where the upper layer film is peeled, an organic developer maybe used, or a peeling liquid may be separately used. As the peelingliquid, a solvent having low permeability to the actinic ray-sensitiveor radiation-sensitive film is preferable. From the viewpoint that thepeeling of the upper layer film and the development of the actinicray-sensitive or radiation-sensitive film can be performed at the sametime, it is preferable that the upper layer film can be peeled off usingthe organic developer. The organic developer used for peeling is notparticularly limited as long as it can dissolve and remove a lowexposure portion of the actinic ray-sensitive or radiation-sensitivefilm.

From the viewpoint of peeling the upper layer film using the organicdeveloper, the dissolution rate of the upper layer film in the organicdeveloper is preferably 1 to 300 nm/sec and more preferably 10 to 100nm/sec.

Here, the dissolution rate of the upper layer film in the organicdeveloper is a rate at which the film thickness is reduced when theupper layer film is formed and then is exposed to the developer. In thepresent invention, the dissolution rate is a rate when the upper layerfilm is dipped in butyl acetate at 23° C.

By adjusting the dissolution rate of the upper layer film in the organicdeveloper to be 1 nm/sec or higher and preferably 10 nm/sec or higher,an effect of reducing the occurrence of development defects afterdeveloping the actinic ray-sensitive or radiation-sensitive film can beobtained. In addition, by adjusting the dissolution rate of the upperlayer film in the organic developer to be 300 nm/sec or lower andpreferably 100 nm/sec or lower, an effect of further improving the lineedge roughness of a pattern after developing the actinic ray-sensitiveor radiation-sensitive film can be obtained due to the effect of reduceduneven exposure during immersion exposure.

The upper layer film may be removed using another well-known developer,for example, an alkali aqueous solution. Specific examples of the alkaliaqueous solution that can be used include an aqueous solution oftetramethylammonium hydroxide.

In addition, the present invention relates to a method of manufacturingan electronic device including the pattern forming method according tothe present invention.

An electronic device that is manufactured using the method ofmanufacturing an electronic device according to the present inventioncan be suitably mounted on electric and electronic apparatuses (homeelectronics, apparatuses relating to office automation (OA) and media,optical apparatuses, and communication apparatuses).

EXAMPLES

Hereinafter, the present invention will be described in detail usingExamples, but the scope of the present invention is not limited thereto.Unless specified otherwise, “%”, “ppb”, and “ppt” are based on mass.

<<Preparation of Treatment Liquid for Manufacturing Semiconductor>>

Hereinafter, synthesis examples of various treatment liquids will bedescribed. However, the present invention is not limited to thefollowing synthesis examples, and the treatment liquid can besynthesized using a well-known method.

Examples 1 to 46 and Comparative Examples 1 and 2

<Purification of Raw Materials and the Like>

Each of raw materials and each of catalysts used in each of thefollowing Examples have a high purity of 99 mass % or higher and waspurified in advance by distillation, ion exchange, filtration, or thelike. In addition, a catalyst used for the following esterificationreaction is sulfuric acid. Sulfuric acid used as the catalyst has apurity of 98 mass % or higher and can be used while dehydrating it to bein a predetermined concentration range by supplying dilute sulfuricacid.

Ultrapure water was purified using a method described in JP2007-254168Aand was used for adjusting the treatment liquid after verifying that thecontent of each element of Na, Ca, and Fe was lower than 10 mass pptwith respect to the total mass of each of the treatment liquids inmeasurement using a SP-ICP-MS method described below.

All the preparation, filling, storage, analysis, and measurement of thetreatment liquids were performed in a clean room satisfying a level ofISO Class 2 or lower. In addition, a container used in Examples was usedafter being cleaned using the treatment liquid according to the presentinvention.

Synthesis Example 1

Synthesis of Butyl Acetate-Containing Treatment Liquid (Treatment Liquid1A)

(Step 1)

Acetic acid and n-butanol were caused to preliminarily react with eachother in the presence of sulfuric acid as a catalyst using a continuoustank reactor. Next, in a continuous reactive distillation column, theobtained reaction solution 1a was caused to react while removing water,which was by-produced as an azeotropic mixture of butyl acetate,n-butanol, and water, from the top of the distillation column to theoutside of the system. As a result, a crude liquid including butylacetate (hereinafter, referred to as “butyl acetate crude liquid”) 1bwas obtained.

(Step 2)

Regarding the butyl acetate crude liquid 1b obtained in the step 1,sulfuric acid was neutralized with alkali. Next, the butyl acetate crudeliquid 1b was cleaned with water, and the water is removed. As a result,a butyl acetate crude liquid 1c was extracted.

(Step 3)

The butyl acetate crude liquid 1e obtained in the step 2 was neutralizedand cleaned with water, and most part of water and sulfuric acid wereseparated from each other using a decanter. Next, a butyl acetate crudeliquid id including butyl acetate, n-butanol, water, sulfuric acid, anda small amount of by-products was supplied to the distillation column inorder to remove low boiling point materials such as n-butanol and waterof impurities. Next, by repeating distillation multiple times, a butylacetate-containing treatment liquid (treatment liquid 1A) as a targetproduct was obtained.

A compound (B) included in the obtained butyl acetate-containingtreatment liquid (treatment liquid 1A) included the following compounds.The content of each of the compounds in the treatment liquid satisfiedthe requirement (b) (refer to Table 2).

Using the same method as in Synthesis Example 1, other butylacetate-containing treatment liquids (treatment liquids 1B to 1Q) weresynthesized. The compound (B) included each of the obtained treatmentliquids was the same as the treatment liquid 1A, and the content of eachof the compounds (B) in the treatment liquid satisfied the requirement(b) (refer to Table 2).

Synthesis Example 2 Synthesis of 1-Hexanol-Containing Treatment Liquid(Treatment Liquid 2A) (Raw Materials and the Like)

1-hexanol was synthesized from the following two steps of reactionformulae.

Al(C₂H₅)₃+6C₂H₄→Al(C₆H₁₃)₃

Al(C₆H₁₃)₃+3/2O₂+3H₂O→3HOC₆H13+Al(OH)₃

(Step 1)

Using a well-known method, Al(C₆H₁₅)₃ polymerized using the first stepof reaction was obtained. Next, by using this Al(C₆H₁₅)₃ as a catalyst,1-hexanol was synthesized using a well-known method in the coexistenceof oxygen and water. The obtained solution was heated at 40° C. for 10hours. As a result, a crude liquid including 1-hexanol (hereinafter,referred to as “1-hexanol crude liquid”) 2a was obtained. Al was removedas aluminum hydroxide.

(Step 2)

The 1-hexanol crude liquid 2a obtained in the step 1 included aprecipitate of Al(OH)₃, and thus Al(OH)₃ was removed by filtering. As aresult, a 1-hexanol crude liquid 2b was obtained.

(Step 3)

The 1-hexanol crude liquid 2b obtained in the step 2 was supplied to thedistillation column in order to remove a substituted isomer of theby-product, higher alcohol, or the like. Next, by repeating distillationmultiple times, a 1-hexanol-containing treatment liquid (treatmentliquid 2A) as a target product was obtained.

A compound (B) included in the 1-hexanol-containing treatment liquid(treatment liquid 2A) included the following compounds. The content ofeach of the compounds in the treatment liquid satisfied the requirement(b) (refer to Table 2).

Synthesis Example 3 Synthesis of 4-Methyl-2-Pentanol-ContainingTreatment Liquid (Treatment Liquid 3A)

(Step 1)

cis-4-methyl-2-pentene was treated using a well-known method in thepresence of diisopinocampheylborane (Ipc₂BH) as a catalyst. As a result,4-methyl-2-pentanol was synthesized. The obtained solution was heated at80° C. for 4 hours. As a result, an intermediate in whichcis-4-methyl-2-pentene and Ipc₂BH were bonded to each other throughboron was obtained, and then a crude liquid including4-methyl-2-pentanol (hereinafter, referred to as “4-methyl-2-pentanolcrude liquid”) 3a was obtained.

(Step 2)

The 4-methyl-2-pentanol crude liquid 3a obtained in the step 1 includedunreacted cis-4-methyl-2-pentene and a substituted isomer as animpurity.

This 4-methyl-2-pentanol crude liquid 3a was supplied to thedistillation column for purification. Next, by repeating distillationmultiple times, a 4-methyl-2-pentanol-containing treatment liquid(treatment liquid 3A) as a target product was obtained.

A compound (B) included in the 4-methyl-2-pentanol-containing treatmentliquid (treatment liquid 3A) included the following compounds. Thecontent of each of the compounds in the treatment liquid satisfied therequirement (b) (refer to Table 2).

Using the same method as in Synthesis Example 3, other4-methyl-2-pentanol-containing treatment liquids (treatment liquids 3Bto 3G) were synthesized. The compound (B) included each of the obtainedtreatment liquids was the same as the treatment liquid 1A, and thecontent of each of the compounds (B) in the treatment liquid satisfiedthe requirement (b) (refer to Table 2).

Synthesis Example 4 Synthesis of Propylene Glycol Monomethyl EtherAcetate (PGMEA)-Containing Treatment Liquid (Treatment Liquid 4A)

(Step 1)

Propylene oxide, methanol, and acetic acid were caused to react witheach other in the presence of sulfuric acid as a catalyst using awell-known method. As a result, PGMEA was synthesized (two-stepsynthesis). The obtained solution was heated at 80° C. for 8 hours. As aresult, a crude liquid including PGMEA (hereinafter, referred to as“PGMEA crude liquid”) 4a was obtained.

(Step 2)

The PGMEA crude liquid 4a obtained in the step 1 included unreactedpropylene oxide, methanol, acetic acid, and a substituted isomer as animpurity.

This PGMEA crude liquid 4a was supplied to the distillation column forpurification. Next, by repeating distillation multiple times, aPGMEA-containing treatment liquid (treatment liquid 4A) as a targetproduct was obtained.

Compounds (B) included in the obtained PGMEA-containing treatment liquid(treatment liquid 4A) were the following compounds. The content of eachof the compounds in the treatment liquid satisfied the requirement (b)(refer to Table 2).

Using the same method as in Synthesis Example 4, other PGMEA-containingtreatment liquids (treatment liquids 4B to 4E) were synthesized. Thecompounds (B) included each of the obtained treatment liquids were thesame as the treatment liquid 4A, and the content of each of thecompounds (B) in the treatment liquid satisfied the requirement (b)(refer to Table 2).

Synthesis Example 5 Synthesis of Isopropanol (IPA)-Containing TreatmentLiquid (Treatment Liquid 5A)

(Step 1)

Using acetone and hydrogen, a reduction reaction of acetone wasperformed in the presence of copper oxide-zinc oxide-aluminum oxide as acatalyst according to a well-known method. The obtained solution washeated at 100° C. for 4 hours. As a result, a crude liquid including IPA(hereinafter, referred to as “IPA crude liquid”) 5 a was obtained.

(Step 2)

The IPA crude liquid 5a included unreacted acetone, a substituted isomeras an impurity, and the catalyst. This IPA crude liquid 5a was suppliedto the distillation column for purification. Next, by repeatingdistillation multiple times, an IPA-containing treatment liquid(treatment liquid 5A) as a target product was obtained.

A compound (B) included in the obtained IPA-containing treatment liquid(treatment liquid 5A) was the following compound. The content of thecompound in the treatment liquid satisfied the requirement (b) (refer toTable 2).

Using the same method as in Synthesis Example 5, other IPA-containingtreatment liquids (treatment liquids 5B to 5E) were synthesized. Thecompound (B) included each of the obtained treatment liquids was thesame as the treatment liquid 5A, and the content of each of thecompounds (B) in the treatment liquid satisfied the requirement (b)(refer to Table 2).

Synthesis Example 6 Synthesis of Ethyl Lactate (EL)-Containing TreatmentLiquid (Treatment Liquid 6A)

(Step 1)

Using lactic acid and ethanol, a crude liquid including ethyl lactate(hereinafter, referred to as “ethyl lactate crude liquid”) 6a wasobtained according to an esterification method described inJP1987-26249A (JP-S62-26249A).

(Step 2)

The ethyl lactate crude liquid 6a obtained in the step 1 included wateror alcohol as a by-product and unreacted ethanol as a raw material.

This obtained ethyl lactate crude liquid 6a was supplied to thedistillation column for purification. Next, by repeating distillationmultiple times, an ethyl lactate-containing treatment liquid (treatmentliquid 6A) was obtained.

Compounds (B) included in the obtained ethyl lactate-containingtreatment liquid (treatment liquid 6A) were the following compounds. Thecontent of each of the compounds in the treatment liquid satisfied therequirement (b) (refer to Table 2).

Using the same method as in Synthesis Example 6, other ethyllactate-containing treatment liquids (treatment liquids 6B to 6E) weresynthesized. The compounds (B) included each of the obtained treatmentliquids were the same as the treatment liquid 6A, and the content ofeach of the compounds (B) in the treatment liquid satisfied therequirement (b) (refer to Table 2).

Synthesis Example 7 Synthesis of Cyclohexanone-Containing TreatmentLiquid (Treatment Liquid 7A)

(Step 1)

Using a method described in JP2007-63209A, monochlorobenzene andhydrogen chloride were obtained from benzene and chlorine. Next, phenoland hydrogen chloride were obtained monochlorobenzene and water. Next, acrude liquid including cyclohexanone (hereinafter, referred to as“cyclohexanone crude liquid”) 7 a was obtained from phenol and hydrogen.

(Step 2)

The cyclohexanone crude liquid 7a obtained from a reaction column in thestep 1 included unreacted benzene, monochlorobenzene, and phenol.

This obtained cyclohexanone crude liquid 7a was supplied to thedistillation column for purification. Next, by repeating distillationmultiple times, a cyclohexanone-containing treatment liquid (treatmentliquid 7A) was obtained.

Compounds (B) included in the cyclohexanone-containing treatment liquid(treatment liquid 7A) were the following compounds. The content of eachof the compounds in the treatment liquid satisfied the requirement (b)(refer to Table 2).

Using the same method as in Synthesis Example 7, anothercyclohexanone-containing treatment liquid (treatment liquid 7E) wassynthesized. In addition, regarding the treatment liquids 7B to 7D and7F to 7G, the crude liquids 7a were purified using a method describedbelow. The compounds (B) included each of the obtained treatment liquidswas the same as the treatment liquid 7A, and the content of each of thecompounds (B) in the treatment liquid satisfied the requirement (b)(refer to Table 2).

Synthesis Example 8 Synthesis of Propylene Glycol Monomethyl Ether(PGME)-Containing Treatment Liquid (Treatment Liquid 8A)

(Step 1)

Using a method described in JP2008-208035A, methanol and propylene oxidewere caused to react with each other at 90° C. to 110° C. As a result, acrude liquid including PGME (hereinafter, referred to as “PGME crudeliquid”) 8 a was obtained.

(Step 2)

The PGME crude liquid 8a obtained from a reaction column in the step 1included unreacted methanol, propylene oxide, acetic acid, and tertiaryamine as a catalyst.

The obtained PGME crude liquid 8a was supplied to the distillationcolumn for purification. Next, by repeating distillation multiple times,a PGME-containing treatment liquid (treatment liquid 8A) was obtained.

Compounds (B) included in the obtained PGME-containing treatment liquid(treatment liquid 8A) were the following compounds. The content of eachof the compounds in the treatment liquid satisfied the requirement (b)(refer to Table 2).

Synthesis Example 9

Synthesis of Methyl 3-Methoxypropionate (MMP)-Containing TreatmentLiquid (Treatment Liquid 8A)

(Step 1)

Using a method described in JP2007-63209A, methanol, potassiumt-butoxide (Kot-Bu) as a basic catalyst, and 74.0 g (0.86 mol) of methylacrylate were weighed and were slowly added dropwise from a droppingfunnel for about 1 hour. At this time, in a case where a small amount ofmethyl acrylate was added dropwise, heat was generated. Therefore, thereaction temperature was controlled at 40° C. while cooling the solutionusing iced water. After completion of the dropwise addition, thesolution was heated and stirred at 40° C. for 1 hour, and the totalreaction time was 2 hours.

Next, phosphoric acid was added, and the solution was stirred at roomtemperature for 30 minutes after verifying that the solution was neutralusing pH test paper. After the neutralization, a solid matter of aneutral salt of the catalyst was separated by suction filtration. As aresult, a crude liquid including MMP (hereinafter, referred to as “MMPcrude liquid”) 9a was obtained.

(Step 2)

The MMP crude liquid 9a obtained from a reaction column in the step 1included unreacted methanol and methyl acrylate.

The obtained MMP crude liquid 9a was supplied to the distillation columnfor purification. Next, by repeating distillation multiple times, anMMP-containing treatment liquid (treatment liquid 9A) was obtained.

Compounds (B) included in the obtained MMP-containing treatment liquid(treatment liquid 9A) were the following compounds. The content of eachof the compounds in the treatment liquid satisfied the requirement (b)(refer to Table 2).

The obtained treatment liquids 1A to 1Q, 2A, 3A to 3G, 4A to 4E, 5A to5E, 6A to 6E, 7A to 7G, 8A, and 9A are shown below in Tables 1-1 to 1-6.Hereinafter, Tables 1-1 to 1-6 will be collectively referred to as Table1.

[Measurement Using SP-ICP-MS Method]

1) Preparation of Standard Material

Ultrapure water was weighed and charged into a clean glass container,and measurement target metal particles having a median size of 50 nmwere added thereto such that the concentration was 10000 atoms/ml. Next,the solution was treated using an ultrasonic cleaning machine for 30minutes to obtain a dispersion. This dispersion was used as a standardmaterial for transport efficiency measurement.

2) SNP-ICP-MS Device Used

Manufacturer: PerkinElmer

Model: NexION 350S

3) Measurement Conditions of SNP-ICP-MS

In SNP-ICP-MS, the measurement target liquid was aspirated at about 0.2mL/min using a PFA coaxial nebulizer formed of PFA, a cyclonic spraychamber formed of quartz, and a torch injector having an inner diameterof 1 mm formed of quartz. The addition amount of oxygen was set as 0.1L/min, the plasma power was set as 1600 W, and the inside of the cellwas purged using ammonia gas. The temporal resolution was set as 50 μsfor analysis.

The content of metal particles and the content of metal atoms weremeasured using the following analysis software manufactured by themanufacturers.

-   -   Content of Metal Particles: Syngistix Nano Application Module        for “SP-ICP-MS”, nanoparticle analysis    -   Content of Metal Atoms: Syngistix for ICP-MS Software

The results are shown in Table 1 below.

[Measurement of Contents of Compound (A), Compound (B), and InorganicMatter (C)]

Each of components used in each of Examples and each of ComparativeExamples was measured using a gas chromatograph/mass spectrometer(GC/MS), a liquid chromatograph/mass spectrometer (LC/MS), nuclearmagnetic resonance (NMR), and ion chromatography (IC). The organicmatter measurement was performed using GC/MS, LC/MS, and NMR, and theinorganic matter analysis was performed using IC.

[GC/MS] (Gas Chromatography-Mass Spectrometer)

(Measurement Conditions)

Device: “GCMS-2020” (manufactured by Shimadzu Corporation)

[LC/MS] (Liquid Chromatograph/Mass Spectrometer)

(Measurement Conditions)

Device: “UPLC—H-Class, Xevo G2-XS Qtof” (manufactured by Thermo FisherScientific Inc.)

[NMR] (Nuclear Magnetic Resonance)

(Measurement Conditions)

Device: AL400 (manufactured by JEOL Ltd.)

Measurement nucleus: ¹H

Solvent: CDCl₃

[IC] (ion chromatography)

(Measurement Conditions)

Device: “HIC-SP” (manufactured by Shimadzu Corporation)

The content of each of the compounds is shown in Table 1 below.

In “Inorganic Matter (C)” of Table 1, the columns “S”, “Al”, “B”, “N”,and “K” represent the content of an inorganic matter including S, thecontent of an inorganic matter including Al, the content of an inorganicmatter including B, the content of an inorganic matter including N, andthe content of an inorganic matter including K, respectively.

[Measurement of Dissolution Rate (ER) of Resist Film]

An organic antireflection film ARC29A (manufactured by Nissan ChemicalIndustries Ltd.) was applied to a silicon wafer and was baked at 205° C.for 60 seconds to form an antireflection film having a thickness of 78nm. Next, a commercially available product FAiRS-9101A12 (ArF resistcomposition, manufactured by Fujifilm Electronic Materials Co., Ltd.)was applied using a spin coater and was baked at 100° C. for 60 seconds.The entire surface of the obtained wafer was exposed at 25 [mJ/cm²]using an ArF excimer laser scanner (NA: 0.75). Next, the wafer washeated at 120° C. for 60 seconds. This wafer was cut into a size of 2cm×2 cm and was dipped in each of the treatment liquids shown in Table 1at 23° C. for 10 minutes. The film thickness was measured before andafter dipping by optical ellipsometry for film thickness measurement,and the dissolution rate (ER) was calculated.

The results are shown in Table 1.

[Defect Suppressing Performance (Measurement of Number of Defects)]Using a wafer surface inspection device (SP-5, manufactured byKLA-Tencor Corporation), the number of particles (hereinafter, referredto as “defects”) having a diameter of 32 nm or more present on a siliconsubstrate surface having a diameter of 300 mm was calculated. Next, thissilicon substrate was set on a spin discharge device, and varioustreatment liquids shown in Table 1 were discharged to the surface of thesilicon substrate at a flow rate of 1.5 L/min while rotating the siliconsubstrate. Next, the silicon wafer was rinsed and dried. Regarding theobtained sample, the number of defects present on the silicon substratesurface was measured again using the device (SP-5), and a differencebetween the measured value and the initial value was calculated as thenumber of defects. The obtained number of defects was evaluated based onthe following standards, and the results thereof are shown in Table 1.In the following standards, the evaluation D represents that theperformance of suppressing defects that is required for the treatmentliquid for manufacturing a semiconductor is achieved.

A: the number of defects was 50 or less

B: the number of defects was more than 50 and 100 or less

C: the number of defects was more than 100 and 500 or less

D: the number of defects was more than 500 and 1000 or less

E: the number of defects was more than 1000

TABLE 1 Inorganic Treatment Content (A) Compound (B) Compound(B) (C)(ppb) Matter P Value Q Value Example Liquid Kind Content Total ContentB1 B2 B3 S Al B N K (C)/(B) (A)/(B) Example 1 Treatment Butyl Acetate99.999999%  0.0000001% 0.00000005% 0.00000005% 0.01 — — — — 10⁻² 10⁹Liquid1A Example 2 Treatment Butyl Acetate 99.999999%  0.0000001%0.00000006% 0.00000004% 0.01 — — — — 10⁻² 10⁹ Liquid1B Example 3Treatment Butyl Acetate 99.999999%  0.0000001% 0.00000004% 0.00000006%0.01 — — — — 10⁻² 10⁹ Liquid1C Example 4 Treatment Butyl Acetate99.999999%  0.0000001% 0.00000007% 0.00000003% 0.01 — — — — 10⁻² 10⁹Liquid1D Example 5 Treatment Butyl Acetate    99.999%  0.0000001%   0.00005%   0.00005% 0.01 — — — — 10⁻⁵ 10⁶ Liquid1E Example 6Treatment Butyl Acetate 99.999999%     0.0001% 0.00000003% 0.00000007%0.001 — — — — 10⁻³ 10⁹ Liquid1F Example 7 Treatment Butyl Acetate99.999999%  0.0000001% 0.00000005% 0.00000005% 1 — — — — 10⁰ 10⁹Liquid1G Example 8 Treatment Butyl Acetate 99.999999%  0.0000001%0.00000005% 0.00000005% 100 — — — — 10² 10⁹ Liquid1H Example 9 TreatmentButyl Acetate 99.999999%  0.0000001% 0.00000001% 0.00000009% 1000 — — —— 10³ 10⁹ Liquid11 Example 10 Treatment Butyl Acetate 99.999999% 0.0000001% 0.00000002% 0.00000008% — — — — — 10⁻² 10⁹ Liquid1J Example11 Treatment 1—Hexanol 99.999999%  0.0000001% 0.00000001% 0.00000009% —0.01 — — — 10⁻² 10⁹ Liquid2A Example 12 Treatment 4-Methyl-2- 99.999999% 0.0000001% 0.00000008% 0.00000002% — — 0.01 — — 10⁻² 10⁹ Liquid3APentanol Example 13 Treatment 4-Methyl-2- 99.999999%  0.0000001%0.00000008% 0.00000002% — — 0.01 — — 10⁻² 10⁹ Liquid3B Pentanol Example14 Treatment 4-Methyl-2- 99.999999%  0.0000001% 0.00000006% 0.00000004%— — 0.01 — — 10⁻² 10⁹ Liquid3C Pentanol Example 15 Treatment PGMEA99.999999%  0.0000001% 0.00000004% 0.00000006% — — 0.01 — — 10⁻² 10⁹Liquid4A Example 16 Treatment IPA 99.999999%  0.0000001% 0.00000010% — —0.01 — — 10⁻² 10⁹ Liquid5A Example 17 Treatment Ethyl Lactate 99.999999% 0.0000001% 0.00000005% 0.00000005% 0.01 — — — — 10⁻² 10⁹ Liquid 6AExample 18 Treatment Cyclohexanone 99.999999%  0.0000001% 0.00000005%0.00000002% 0.00000003% — 0.01 — — — 10⁻² 10⁹ Liquid 7A Example 19Treatment Butyl Acetate   99.99%   0.000003%   0.000002%  0.000001%0.001 — — — — 3 × 10⁻⁵ 3 × 10⁷ Liquid 1M Example 20 Treatment ButylAcetate   99.99%  0.0000003%  0.0000002%  0.0000001% 0.001 — — — — 3 ×10⁻⁴ 3 × 10⁸ Liquid 1N Example 21 Treatment Butyl Acetate   99.99%0.00000003% 0.00000002% 0.00000001% 0.0001 — — — — 3 × 10⁻⁴ 3 × 10⁹Liquid 10 Example 22 Treatment P Butyl Acetate   99.99% 0.00000003%0.00000002% 0.00000001% 0.0001 — — — — 3 × 10⁻⁴ 3 × 10⁹ Liquid 1 Example23 Treatment Butyl Acetate   99.99% 0.00000003% 0.00000002% 0.00000001%1 — — — — 3 × 10⁹ 3 × 10⁹ Liquid 1Q Example 24 Treatment 4-Methyl-2-  99.99%  0.0000003%  0.0000002%  0.0000001% — — 0.001 — — 3 × 10⁻⁴ 3 ×10⁸ Liquid 3D Pentanol Example 25 Treatment 4-Methyl-2-   99.99%0.00000003% 0.00000002% 0.00000001% — — 0.0001 — — 3 × 10⁻⁴ 3 × 10⁹Liquid 3E Pentanol Example 26 Treatment 4-Methyl-2-   99.99% 0.00000003%0.00000002% 0.00000001% — — 0.0001 — — 3 × 10⁻⁴ 3 × 10⁹ Liquid 3FPentanol Example 27 Treatment 4-Methyl-2-   99.99% 0.00000003%0.00000002% 0.00000001% — — 1 — — 3 × 10⁹ 3 × 10⁹ Liquid 3G PentanolExample 28 Treatment PGMEA   99.99%  0.0000003%  0.0000002%  0.0000001%0.001 — — — — 3 × 10⁻⁴ 3 × 10⁸ Liquid 4B Example 29 Treatment PGMEA  99.99% 0.00000003% 0.00000002% 0.00000001% 0.0001 — — — — 3 × 10⁻⁴ 3 ×10⁹ Liquid 4C Example 30 Treatment PGMEA   99.99% 0.00000003%0.00000002% 0.00000001% 0.0001 — — — — 3 × 10⁻⁴ 3 × 10⁹ Liquid 4DExample 31 Treatment PGMEA   99.99% 0.00000003% 0.00000002% 0.00000001%1 — — — — 3 × 10⁰ 3 × 10⁹ Liquid 4E Example 32 Treatment IPA   99.99%0.00000002%  0.0000002% — — 0.001 — — 5 × 10⁻⁴ 5 × 10⁸ Liquid 5B Example33 Treatment IPA    99.99% 0.00000002% 0.00000002% — — 0.0001 — — 5 ×10⁻⁴ 5 × 10⁹ Liquid 5C Example 34 Treatment IPA    99.99% 0.00000002%0.00000002% — — 0.0001 — — 5 × 10⁻⁴ 5 × 10⁹ Liquid 5D Example 35Treatment IPA    99.99% 0.00000002% 0.00000002% — — — — — 5 × 10⁰ 5 ×10⁹ Liquid 5E Example 36 Treatment Ethyl Lactate    99.99%  0.0000003% 0.0000002%  0.0000001% 0.001 — — — — 3 × 10⁻⁴ 3 × 10⁸ Liquid 6B Example37 Treatment Ethyl Lactate    99.99% 0.00000003% 0.00000002% 0.00000001%0.0001 — — — — 3 × 10⁻⁴ 3 × 10⁹ Liquid 6C Example 38 Treatment EthylLactate    99.99% 0.00000003% 0.00000002% 0.00000001% 0.0001 — — — — 3 ×10⁻⁴ 3 × 10⁹ Liquid 6D Example 39 Treatment Ethyl Lactate    99.99%0.00000003% 0.00000002% 0.00000001% 1 — — — — 3 × 10⁰ 3 × 10⁹ Liquid 6EExample 40 Treatment Cyclohexanone    99.99%  0.000001%  0.0000002% 0.0000001%  0.0000007% — 0.001 — — — 10⁻⁴ 10⁸ Liquid 7B Example 41Treatment Cyclohexanone    99.99%  0.0000001% 0.00000002% 0.00000001%0.00000007% — 0.0001 — — — 10⁻⁴ 10⁹ Liquid 7C Example 42 TreatmentCyclohexanone    99.99%  0.0000001% 0.00000002% 0.00000001% 0.00000007%— 0.0001 — — — 10⁻⁴ 10⁹ Liquid 7D Example 43 Treatment Cyclohexanone   99.99%  0.000001%  0.0000002%  0.0000001%  0.0000007% — 0.1 — — —10⁻² 10⁸ Liquid 7E Example 44 Treatment Cyclohexanone    99.99% 0.0000001% 0.00000002% 0.00000001% 0.00000007% — 0.01 — — — 10⁻2 10⁹Liquid 7F Example 45 Treatment Cyclohexanone    99.99%  0.0000001%0.00000002% 0.00000001% 0.00000007% — 1 — — — 100 10⁹ Liquid 7G Example46 Treatment PGME    99.99% 0.00000003% 0.00000002% 0.00000001% — — —0.0001 — 3 × 10⁻⁴ 3 × 10⁹ Liquid 8A Example 47 Treatment MMP    99.99%0.00000003% 0.00000002% 0.00000001% — — — — 0.0001 3 × 10⁻⁴ 3 × 10⁹Liquid 9A Comparative Treatment Butyl Acetate 99.999999%  0.0000001%0.00000001% 0.00000009% 10000 — — — — 10⁴ 10⁹ Example 1 Liquid 1KComparative Treatment Butyl Acetate    99.9%     0.1%      0.5%     0.5%0.001 — — — — 10⁻⁹ 10³ Example 2 Liquid 1L De- Content fect of Supress-Metal Content of Metal ing Treatment Atoms (ppt) Particles (ppt) ERPerform- Example Liquid Na Ca Fe Na Ca Fe (nm/s) ance Example 1Treatment 10 6 3 3 1 1 0.00333 A Liquid 1A Example 2 Treatment 10 6 3 31 1 0.00333 A Liquid 1B Example 3 Treatment 10 6 3 3 1 1 0.00333 ALiquid 1C Example 4 Treatment 10 6 3 3 1 1 0.00333 A Liquid 1D Example 5Treatment 16 9 6 5 2 1 0.01667 B Liquid 1E Example 6 Treatment 20 12 5 95 1 0.02167 B Liquid 1F ppt ppt ppt ppt ppt Example 6 Treatment 4 3 0.51 1 1 0.00333 A Liquid 1F Example 7 Treatment 19 10 7 10 6 4 0.00667 BLiquid 1G Example 8 Treatment 56 32 21 23 15 13 0.01333 C Liquid 1HExample 9 Treatment 123 98 56 85 65 30 0.04167 D Liquid 11 Example 10Treatment 10 6 3 3 1 1 0.00333 A Liquid 1J Example 11 Treatment 8 4 1 21 1 0.00667 A Liquid 2A Example 12 Treatment 20 12 10 9 6 3 0.005 ALiquid 3A Example 13 Treatment 20 12 10 9 6 3 0.005 A Liquid 3B Example14 Treatment 20 12 10 9 6 3 0.005 A Liquid 3C Example 15 Treatment 15 126 6 4 1 0.01333 A Liquid 4A Example 16 Treatment 9 6 3 3 1 1 0.01333 ALiquid 5A Example 17 Treatment 10 5 4 2 2 0.01333 A Liquid 6A Example 18Treatment 13 9 8 4 2 2 0.00333 A Liquid 7A Example 19 Treatment 0.040.03 0.05 0.01 0.01 0.01 0.00133 A Liquid 1M Example 20 Treatment 0.020.04 0.02 0.02 0.02 0.02 0.00133 A Liquid 1N Example 21 Treatment 0.0050.003 0.006 0.001 0.001 0.001 0.00133 A Liquid 1O Example 22 Treatment0.003 0.002 0.003 0.001 0.001 0.001 0.00133 A Liquid 1P Example 23Treatment 19 10 7 10 6 4 0.00667 B Liquid 1Q Example 24 Treatment 0.020.04 0.02 0.02 0.02 0.02 0.00133 A Liquid 3D Example 25 Treatment 0.0050.003 0.006 0.001 0.001 0.001 0.00133 A Liquid 3E Example 26 Treatment0.003 0.002 0.003 0.001 0.001 0.001 0.00133 A Liquid 3F Example 27Treatment 19 10 7 10 6 4 0.00667 B Liquid 3G Example 28 Treatment 0.020.04 0.02 0.02 0.02 0.02 0.00133 A Liquid 4B Example 29 Treatment 0.0050.003 0.006 0.001 0.001 0.001 0.00133 A Liquid 4C Example 30 Treatment0.003 0.002 0.003 0.001 0.001 0.001 0.00133 A Liquid 4D Example 31Treatment 19 10 7 10 6 4 0.00667 B Liquid 4E Example 32 Treatment 0.020.04 0.02 0.02 0.02 0.02 0.00133 A Liquid 5B Example 33 Treatment 0.0050.003 0.006 0.001 0.001 0.001 0.00133 A Liquid 5C Example 34 Treatment0.003 0.002 0.003 0.001 0.001 0.001 0.00133 A Liquid 5D Example 35Treatment 19 10 7 10 6 4 0.00667 B Liquid 5E Example 36 Treatment 0.020.04 0.02 0.02 0.02 0.02 0.00133 A Liquid 6B Example 37 Treatment 0.0050.003 0.006 0.001 0.001 0.001 0.00133 A Liquid 6C Example 38 Treatment0.003 0.002 0.003 0.001 0.001 0.001 0.00133 A Liquid 6D Example 39Treatment 19 10 7 10 6 4 0.00667 B Liquid 6E Example 40 Treatment 0.020.04 0.02 0.02 0.02 0.02 0.00133 A Liquid 7B Example 41 Treatment 0.0050.003 0.006 0.001 0.001 0.001 0.00133 A Liquid 7C Example 42 Treatment0.003 0.002 0.003 0.001 0.001 0.001 0.00133 A Liquid 7D Example 43Treatment 2 4 2 2 2 2 0.00133 B Liquid 7E Example 44 Treatment 0.0050.00 0.05 0.02 0.01 0.02 0.00133 A Liquid 7F Example 45 Treatment 0.020.02 0.03 0.01 0.01 0.01 0.00133 A Liquid 7G Example 46 Treatment 0.0030.002 0.003 0.001 0.001 0.001 0.00133 A Liquid 8A Example 47 Treatment0.003 0.002 0.003 0.001 0.001 0.001 0.00133 A Liquid 9A ComparativeTreatment 1135 1083 936 321 264 185 0.04167 E Example 1 Liquid 1KComparative Treatment 860 620 312 256 163 149 0.01333 E Example 2 Liquid1L

TABLE 2 Treatment Compound (B) Liquid Compound (A) B1 B2 B3 1A TO 1QButyl Acetate

2A 1-Hexanol

3A TO 3G 4-Methyl-2-Pentanol

4A TO 4E PGMEA

5A TO 5E IPA

6A TO 6E Butyl Acetate

7A TO 7G Ethyl Acetate

8A PGME

9A MMP

<Purification Method of Treatment Liquids 7B to 7D and 7F to 7G>

By purifying the cyclohexanone (CyHx) crude liquid 7a obtained asdescribed above using the following method, the treatment liquids 7B to7D and 7F to 7G shown in Table 1 were obtained.

In the purification method, a manufacturing device having a structurecorresponding to the manufacturing device shown in FIG. 2 was used, andthe number of distillation steps or a filtration method (pore size,material) was selected so as to obtain the treatment liquids 7B to 7Dand 7F to 7G having different purities. In the filtration method, as afilter used in the filtration device included in the manufacturingdevice, a filter shown in Table 3 below was used to adjust the purity ofthe treatment liquid.

Before purifying the crude liquid 7a using the purification method, themanufacturing device was cleaned with a cleaning liquid. In a cleaningmethod, the treatment liquid 7E (cyclohexanone) shown in Table 1 wasused as the cleaning liquid, and the treatment liquid 7E was circulatedthrough the filter 10 times. This operation was set as one set and wasrepeated three times.

Treatment Defect Cleaning Liquid Filter Liquid Suppressing of FilterFirst Second Third after Purification Performance Example 40 CyHx(Treatment Liquid 7E) IEX-PTFE(10 nm) PTFE(10 nm) UPE(3 nm) CyHx(Treatment Liquid 7B) A surfric acid Example 41 CyHx (Treatment Liquid7E) IEX-PTFE(10 nm) PTFE(10 nm) Nylon(5 nm) surfric acid CyHx (TreatmentLiquid 7C) A Example 42 CyHx (Treatment Liquid 7E) IEX-PTFE(10 nm)PTFE(10 nm) Nylon(5 nm) CyHx (Treatment Liquid 7D) A carboxylic acidExample 44 CyHx (Treatment Liquid 7E) PTFE(10 nm) Nylon(5 nm) CyHx(Treatment Liquid 7F) A Example 45 CyHx (Treatment Liquid 7E) Nylon(5nm) CyHx (Treatment Liquid 7G) A

In Table 3, Nylon, polytetrafluoroethylene (PTFE), and ultra highmolecular weight polyethylene (UPE) represent a filter including nylonas a major component, a filter including PTFE as a major component, anda filter including UPE as a major component, respectively. In addition,IEX-PTFE sulfuric acid and IEX-PTFE carboxylic acid (where IEXrepresents an ion exchange group) represent a filter in which thesurface of PTFE was modified with sulfonic acid and a filter in whichthe surface of PTFE was modified with carboxylic acid, respectively.

<Preparation of Resist Patterns>

[Examples 101 to 112 and Comparative Examples 101 and 102] An organicantireflection film ARC29A (manufactured by Nissan Chemical IndustriesLtd.) was applied to a silicon wafer and was baked at 205° C. for 60seconds to form an antireflection film having a thickness of 78 nm.Next, a commercially available product FAiRS-9101A12 (ArF resistcomposition, manufactured by Fujifilm Electronic Materials Co., Ltd.)was applied to the organic antireflection film using a spin coater andwas baked at 100° C. for 60 seconds. As a result, a resist film having athickness of 150 nm was formed. The obtained wafer was exposed at 25[mJ/cm²] using an ArF excimer laser scanner (NA: 0.75) in a patternshape. Next, the wafer was heated at 120° C. for 60 seconds and then wasdeveloped (negative type development) using each of the treatmentliquids shown in Table 4 for 30 seconds. As a result, an L/S pattern wasobtained.

After the development, the pattern according to each of Examples 105 to107 was rinsed using each of the treatment liquids shown in Table 4 for30 seconds. As a result, an L/S pattern was obtained.

[Examples 113 to 119] An organic antireflection film ARC29A(manufactured by Nissan Chemical Industries Ltd.) was applied to asilicon wafer and was baked at 205° C. for 60 seconds to form anantireflection film having a thickness of 78 nm. Next, in order toimprove coating properties, a pre-wet step of applying the treatmentliquid shown in Table 3 in advance was performed. Next, a commerciallyavailable product FAiRS-9101A12 (ArF resist composition, manufactured byFujifilm Electronic Materials Co., Ltd.) was applied using a spin coaterand was baked at 100° C. for 60 seconds. As a result, a resist filmhaving a thickness of 150 nm was formed. The obtained wafer was exposedat 25 [mJ/cm²] using an ArF excimer laser scanner (NA: 0.75) in apattern shape. Next, the wafer was heated at 120° C. for 60 seconds andthen was developed (negative type development) using each of thetreatment liquids shown in Table 4 for 30 seconds. The obtained patternwas rinsed with the treatment liquid shown in Table 1. As a result, anL/S pattern was obtained.

[Lithographic Performance]

After the formation of the pattern, a line pattern upper surface and aspace portion were observed using a critical dimension scanning electronmicroscope (S9380 II, manufactured by Hitachi Ltd.). The less the valueof the dimension of the formed pattern, the better the performance. Inthe following standards, the evaluation D achieves the lithographicperformance required for the resist pattern.

The evaluation results are shown in Table 4.

A: L/S=less than 80 nm

B: L/S=80 nm or more and less than 120 nm

C: L/S=120 nm or more and less than 150 nm

D: L/S=150 nm or more and less than 200 nm

E: L/S=200 nm or more

TABLE 4 Lithographic Pre-Wet Step Development Step Rinsing StepPerformance Example 101 Treatment Liquid 1A B (Butyl Acetate) Example102 Treatment Liquid 2A C (1-Hexanol) Example 103 Treatment Liquid 3A B(4-Methyl-2-Pentanol) Example 104 Treatment Liquid 6A C (Ethyl Acetate)Example 105 Treatment Liquid 1B Treatment Liquid 3B B (Butyl Acetate)(4-Methyl-2-Pentanol) Example 106 Treatment Liquid 1C Treatment Liquid5A B (Butyl Acetate) (IPA) Example 107 Treatment Liquid 1D TreatmentLiquid 4A B (Butyl Acetate) (PGMEA) Example 108 Treatment Liquid 1E C(Butyl Acetate) Example 109 Treatment Liquid 1F C (Butyl Acetate)Example 109 Treatment Liquid 1F B (Butyl Acetate) Example 110 TreatmentLiquid 1G C (Butyl Acetate) Example 111 Treatment Liquid 1H C (ButylAcetate) Example 112 Treatment Liquid 1I D (Butyl Acetate) Example 113Treatment Liquid 7A Treatment Liquid 1J Treatment Liquid 3C A(Cyclohexanone) (Butyl Acetate) (4-Methyl-2-Pentanol) Example 114Treatment Liquid 7D Treatment Liquid 1P Treatment Liquid 3F A(Cyclohexanone) (Butyl Acetate) (4-Methyl-2-Pentanol) Example 115Treatment Liquid 7D Treatment Liquid 4D Treatment Liquid 3F A(Cyclohexanone) (PGMEA) (4-Methyl-2-Pentanol) Example 116 TreatmentLiquid 7D Treatment Liquid 5D Treatment Liquid 3F A (Cyclohexanone)(IPA) (4-Methyl-2-Pentanol) Example 117 Treatment Liquid 7D TreatmentLiquid 6D Treatment Liquid 3F A (Cyclohexanone) (Ethyl Acetate)(4-Methyl-2-Pentanol) Example 118 Treatment Liquid 4D Treatment Liquid1P Treatment Liquid 3F A (PGMEA) (Butyl Acetate) (4-Methyl-2-Pentanol)Example 119 Treatment Liquid 9A Treatment Liquid 1P Treatment Liquid 3FA (MMP) (Butyl Acetate) (4-Methyl-2-Pentanol) Comparative TreatmentLiquid 1K E Example 101 (Butyl Acetate) Comparative Treatment Liquid 1LE Example 102 (Butyl Acetate)

Examples 201 and 202 and Comparative Example 201

Dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.)was prepared, was purified using a method described in JP2007-254168A,and was used for adjusting the treatment liquid after verifying that thecontent of each of Na, Ca, and Fe in the treatment liquid was lower than10 mass ppb.

Example 201

90.5 parts by mass of the treatment liquid 1A according to Example 1 and9.5 parts by mass of dimethyl sulfoxide obtained as described above weremixed with each other. As a result, a treatment liquid X-1 was prepared.

The treatment liquid X-1 included two or more compounds (B) satisfyingthe requirement (b) and the inorganic matter (C) in addition to thetreatment liquid 1A and the dimethyl sulfoxide, the total content of thecompound (B) was 10⁻¹⁰ to 0.1 mass %, and a ratio P of the inorganicmatter (C) to the compounds (B) represented by Expression I was 10³ to10⁻⁶. In a case where the treatment liquid X-1 was evaluated using thesame method as in Example 1 and Example 101, the same defect suppressingperformance as in Example 1 and the same lithographic performance as inExample 101 were obtained.

Example 202

95 parts by mass of the treatment liquid 1A according to Example 1 and 5parts by mass of dimethyl sulfoxide obtained as described above weremixed with each other. As a result, a treatment liquid X-2 was prepared.

The treatment liquid X-2 included two or more compounds (B) satisfyingthe requirement (b) and the inorganic matter (C) in addition to thetreatment liquid 1A and the dimethyl sulfoxide, the total content of thecompound (B) was 10⁻¹⁰ to 0.1 mass %, and a ratio P of the inorganicmatter (C) to the compounds (B) represented by Expression I was 10³ to10⁻⁶. In a case where the treatment liquid X-2 was evaluated using thesame method as in Example 1 and Example 101, the same defect suppressingperformance as in Example 1 and the same lithographic performance as inExample 101 were obtained.

Comparative Example 201

85 parts by mass of the treatment liquid 1A according to Example 1 and15 parts by mass of dimethyl sulfoxide obtained as described above weremixed with each other. As a result, a treatment liquid X-3 was prepared.In a case where the treatment liquid X-3 was evaluated using the samemethod as in Example 1 and Example 101, the same result as in Example 1was obtained. However, the treatment liquid remained after rinsing, anda long period of time was required for drying.

Examples 301 to 307

A first treatment liquid and a second treatment liquid shown in Table 5below were mixed with each other at a ratio shown in Table 4. As aresult, treatment liquids 101 to 106 were prepared. In addition, atreatment liquid 107 shown in Table 5 was the treatment liquid 9Aprepared as described above. Regarding each of the treatment liquids 101to 107, the defect suppressing performance was evaluated using the samemethod as described above. In addition, in a case where each of thetreatment liquids was used as the pre-wet liquid, the resist savingperformance was evaluated. In addition, in a case where each of thetreatment liquids was used as the rinsing liquid after ashing or afterp-CMP, the performance was evaluated. The results are shown in Table 5.

[Resist Saving Performance]

In a case where each of the treatment liquids was used as the pre-wetliquid, the resist saving performance was evaluated using the followingmethod. In this specification, higher resist saving performancerepresent a state where the uniformity and the film thicknesscontrollability were excellent. It can be seen that, in this state,deterioration of the lithographic performance and the occurrence ofdefects can be suppressed.

The resist composition 1 used is as follows.

<Resist Composition 1>

The following acid decomposable resin, a photoacid generator, aquencher, a hydrophobic resin, and a solvent were mixed with each otherto prepare a resist composition 1 having a solid content concentrationof 3.5 mass %.

The following acid decomposable resin: 100 parts by mass

The weight-average molecular weight (Mw) of the acid decomposable resinwas 7500. and a numerical value described in each repeating unit refersto mol %.

The following photoacid generator: 8 parts by mass

The following four kinds of quenchers: 5 parts by mass (total)

The mass ratio of the quenchers was 0.1:0.3:0.3:0.2 in order from theleft. Among the four kinds of quenchers, the weight-average molecularweight (Mw) of the right polymer type quencher was 5000. In addition, anumerical value described in each repeating unit represents a molarratio.

The following two kinds of hydrophobic resins: 4 parts by mass (total)

The mass ratio of the hydrophobic resins was 0.5:0.5 in order from theleft. Among the two kinds of hydrophobic resins, the weight-averagemolecular weight (Mw) of the left hydrophobic resin was 7000, and theweight-average molecular weight (Mw) of the right hydrophobic resin was8000. In each of the hydrophobic resins, a numerical value described ineach repeating unit represents a molar ratio.

Solvent 1:

PGMEA (manufactured by Wako Pure Chemical Industries, Ltd.): 3 parts bymass

CyHx (cyclohexanone; manufactured by Wako Pure Chemical Industries,Ltd.): 600 parts by mass

GBL (γ-butyrolactone; manufactured by Wako Pure Chemical Industries,Ltd.): 100 parts by mass

<Resist Composition 2>

A resist composition 2 was prepared under the same conditions as thoseof the resist composition 1, except that the following solvent 2 wasused instead of the solvent 1 (PGMEA:CyHx:GBL=3 parts by mass:600 partsby mass:100 parts by mass).

Solvent 2:

Treatment liquid 4A (PGMEA): 3 parts by mass

Treatment liquid 7D (CyHx): 600 parts by mass

GBL (γ-butyrolactone; manufactured by Wako Pure Chemical Industries,Ltd.): 100 parts by mass

<Uniformity>

First, for comparison, the resist composition 1 (or the resistcomposition 2) was directly applied to a silicon wafer having a diameterof about 30 cm (12 inch) including an antireflection film. For theapplication, a spin coater (trade name: “LITHIUS”, manufactured by TokyoElectron Ltd.) was used. The obtained resist film was baked at 90° C.Regarding the baked resist film, 59 points were mapped using a filmthickness measuring device Lambda Ace (manufactured by Screen HoldingsCo., Ltd.) to verify that coating unevenness did not occur. No coatingunevenness represents a state where there was no unevenness in thethickness of a resist film as a measurement target in a case where 59measurement points in a circular shape were extracted from the resistfilm of the measurement target and the results of measuring thethickness of the resist film at each of the measurement points weretwo-dimensionally disposed for each of the measurement points.

Next, a silicon wafer having a diameter of about 30 cm (12 inch)including an antireflection film was separately prepared, and each ofthe treatment liquids was added dropwise thereto. Next, the same amountof the resist composition 1 (or the resist composition 2) as that usedfor comparison was applied to the silicon wafer and was baked at 90° C.The obtained resist film was observed using the same method as describedabove and verified that coating unevenness did not occur. Next, theamount of the resist composition 1 (or the resist composition 2) usedwas reduced to be 50 mass % or 30 mass % with respect to the amount usedfor comparison, and then the same test as described above was performedto determine whether or not coating unevenness occurred.

The results were evaluated based on the following standards, and theevaluation results are shown in Table 5.

AA: in either case where the amount of the resist composition used wasreduced to be 30 mass % or 50 mass % with respect to the amount used forcomparison, coating unevenness did not occur.

A: in a case where the amount of the resist composition used was reducedto be 50 mass % with respect to the amount used for comparison, coatingunevenness did not occur; however, in a case where the amount of theresist composition used was reduced to be 30 mass % with respect to theamount used for comparison, coating unevenness occurred.

B: in either case where the amount of the resist composition used wasreduced to be 30 mass % or 50 mass % with respect to the amount used forcomparison, coating unevenness occurred.

<Film Thickness Controllability>

Each of the treatment liquids was added dropwise to a silicon waferhaving a diameter of about 30 cm (12 inch) including an antireflectionfilm. Next, the resist composition 1 (or the resist composition 2) wasdirectly applied such that the thickness of the obtained resist film was8.5 nm. For the application, a spin coater (trade name: “LITHIUS”,manufactured by Tokyo Electron Ltd.) was used. The obtained resist filmwas baked at 90° C. Regarding the baked resist film, 59 points weremapped using a film thickness measuring device Lambda Ace (manufacturedby Screen Holdings Co., Ltd.) to obtain a standard deviation(hereinafter, also referred to as “σ”) of the thickness of the resistfilm. Next, 3σ was obtained from the standard deviation.

The results were evaluated based on the following standards, and theevaluation results are shown in Table 5.

A: 3σ was less than 0.15 nm

B: 3σ was 0.15 nm or more and less than 0.2 nm

C: 3σ was 0.2 nm or more

[Rinsing Performance after Removal by Ashing]

The resist composition 1 (or the resist composition 2) was applied tothe silicon wafer, was exposed (50 mJ), and was dried by heating (220°C.). As a result, the 12-inch wafer including the resist film(thickness: 0.5 μm) was prepared. Next, using plasma gas, the resistfilm was removed by ashing under the following conditions. Next, thewafer was cleaned using each of the treatment liquids (treatment liquids101 to 107) shown in Table 5 to remove residues (ashing residues) afterthe removal by ashing. Next, by counting the number of defects in thecleaned wafer using SP-2 (manufactured by KLA-Tencor Corporation), therinsing performance of each of the treatment liquids with respect to theashing residues was evaluated.

[Conditions of Removal by Ashing]

Wafer Temperature: 250° C.

O₂ gas flow rate: 1000 sccm

Pressure: 70 Pa

Microwave power: 1 kW

—Evaluation Standards—

AA: the number of defects was 50 or less

A: the number of defects was more than 50 and 80 or less

B: the number of defects was more than 80 and 100 or less

C: the number of defects was more than 100 and 150 or less

D: the number of defects was more than 150

[Rinsing Performance after p-CMP]

Using CSL9044C (slurry manufactured by FFPS), a surface of SEMATECH 845(copper wiring, barrier metal: TaN, oxide film: TEOS; manufactured bySEMATECH) having a diameter of 12 inch was polished to be planarized.Next, the surface of SEMATECH 845 was finish-polished using BSL8178C(slurry manufactured by FFPS).

Next, the surface of SEMATECH 845 was cleaned using Clean 100(manufactured by Wako Pure Chemical Industries, Ltd.), and each of thetreatment liquids was used as a rinsing liquid. Next, using a patterndefect inspection device (ComPLUS, manufactured by AMAT), the number ofdefects on the pattern of SEMATECH 854 was measured. The results wereevaluated based on the following standards.

—Evaluation Standards—

AA: the number of defects was 50 or less

A: the number of defects was more than 50 and 80 or less

B: the number of defects was more than 80 and 100 or less

C: the number of defects was more than 100 and 150 or less

D: the number of defects was more than 150

TABLE 5 First Treatment Second Treatment Resist Saving PerformanceRinsing Performance after Liquid Liquid Defect Resist Composition 1Resist Composition 2 Removal by Ashing Rinsing Content ContentSuppressing Film Thickness Film Thickness Resist Resist Performance Kind(mass%) Kind (mass%) Performance Uniformity Controllability UniformityControllability Composition 1 Composition 2 after p-CMP ExampleTreatment PGME 30 PGME 70 B A A A A A A A 301 Liquid 101 (Treatment(Treatment Liquid 8A) Liquid 4A) Example Treatment PGME 30 CyHe 70 A AAA AA A A A AA 302 Liquid 102 (Treatment (Treatment Liquid 8A) Liquid 7D)Example Treatment PGME 30 EL 70 A AA A AA A A A AA 303 Liquid 103(Treatment (Treatment Liquid 8A) Liquid 6A) Example Treatment nBA 30PGMEA 70 B A A A A A A A 304 Liquid 104 (Treatment (Treatment Liquid 1P)Liquid 4A) 70 A AA A AA A A A AA Example Treatment nBA 30 CyHe 305Liquid 105 (Treatment (Treatment Liquid 1P) Liquid 7D) Example TreatmentnBA 30 EL 70 A AA A AA A A A AA 306 Liquid 106 (Treatment (TreatmentLiquid 1P) Liquid 6A) Example Treatment MMP 100 A AA A AA A A A AA 307Liquid 107 (Treatment Liquid 9A)

What is claimed is:
 1. A storage container storing a treatment liquidfor manufacturing a semiconductor, the treatment liquid formanufacturing a semiconductor comprising: one compound (A) thatsatisfies the following requirement (a); one compound (B) or two or morecompounds (B) that satisfy the following requirement (b); and oneinorganic matter (C) or two or more inorganic matters (C) having anyelement selected from the group consisting of Al, B, S, N, and K,wherein a total content of the compound (B) in the treatment liquid is10⁻¹⁰ to 0.1 mass %, a ratio P of the inorganic matter (C) to thecompound (B) represented by the following Expression I is 10³ to 10⁻⁶,the requirement (a): a compound that is selected from the groupconsisting of an alcohol compound, a ketone compound, and an estercompound and of which a content in the treatment liquid is 90.0 to99.9999999 mass %, the requirement (b): a compound that is selected fromthe group consisting of an alcohol compound having 6 or more carbonatoms, a ketone compound, an ester compound, an ether compound, and analdehyde compound and of which a content in the treatment liquid is10⁻¹¹ to 0.1 mass %, andP=[Total Mass of Inorganic Matter (C)]/[Total Mass of Compound (B)]  Expression I.
 2. The storage container according to claim 1, wherein aliquid contact portion in contact with the treatment liquid formanufacturing a semiconductor is formed of a fluororesin.
 3. The storagecontainer according to claim 1, wherein a liquid contact portion incontact with the treatment liquid for manufacturing a semiconductor isformed of stainless steel.
 4. The storage container according to claim3, wherein a mass ratio Cr/Fe of a Cr content to an Fe content in thestainless steel forming the liquid contact portion is higher than 0.5and lower than 3.5.